Safe Handling Guidelines for Methanol
GPIC is a Responsible Care Company Responsible Care is the cultural foundation of GPIC’s commitment to health, safety, security, communities and the environment. Although there are hazards associated with methanol, they can be managed to minimise potential risks to people and the environment during the life cycle of methanol.
GPIC is a Responsible Care Company Responsible Care is the cultural foundation of GPIC’s commitment to health, safety, security, communities and the environment. Although there are hazards associated with methanol, they can be managed to minimise potential risks to people and the environment during the life cycle of methanol.
President’s Message In GPIC, we are committed to upholding our mission and endeavour to use only the best practices in all our manufacturing processes, systems and procedures. As a socially responsible company, we continuously strive to maintain the GPIC facility in a safe, healthy and environmentally friendly manner. Our commitment towards a responsible business management process across the lifecycle of our product’s, has resulted in our achievement of the highest quality products to the complete satisfaction of our worldwide customers and end users.
Our product handling and export facility is the main link between our process and export activities. This facility is part of critical operations that require vigilance and strict adherence to safety, health and environmental regulations and best practices. Such compliance will reduce the risk of injuries and prevent environmental pollution and ensures the delivery of best product quality throughout the supply chain cycle down to the end user, in the safest and most efficient manner. This booklet endorses our proactive product stewardship management, reflecting our
commitments, as an accredited Responsible Care (RC 14001) organisation, as well as an active member of the industrial community on an international level; toward Protect and Sustain initiatives. The booklet outlines the objective of increasing awareness of all personnel involved in the field of handling and transporting methanol including customers. It also highlights the importance of safety, security and hygiene and other key characteristics and aspects related to this product, namely, storage, transfer and export operations. Dr. Abdulrahman Jawahery GPIC President
President’s Message In GPIC, we are committed to upholding our mission and endeavour to use only the best practices in all our manufacturing processes, systems and procedures. As a socially responsible company, we continuously strive to maintain the GPIC facility in a safe, healthy and environmentally friendly manner. Our commitment towards a responsible business management process across the lifecycle of our product’s, has resulted in our achievement of the highest quality products to the complete satisfaction of our worldwide customers and end users.
Our product handling and export facility is the main link between our process and export activities. This facility is part of critical operations that require vigilance and strict adherence to safety, health and environmental regulations and best practices. Such compliance will reduce the risk of injuries and prevent environmental pollution and ensures the delivery of best product quality throughout the supply chain cycle down to the end user, in the safest and most efficient manner. This booklet endorses our proactive product stewardship management, reflecting our
commitments, as an accredited Responsible Care (RC 14001) organisation, as well as an active member of the industrial community on an international level; toward Protect and Sustain initiatives. The booklet outlines the objective of increasing awareness of all personnel involved in the field of handling and transporting methanol including customers. It also highlights the importance of safety, security and hygiene and other key characteristics and aspects related to this product, namely, storage, transfer and export operations. Dr. Abdulrahman Jawahery GPIC President
Contents
DISCLAIMER MESSAGE The guidelines illustrated in this book are a summary of practices that are proven to be appropriate and suitable for the handling, transport and storage of ammonia and GPIC shall not be liable for errors, omissions or incorrect use of these guidelines. The mentioned data are based on the current state of knowledge and insights, and cannot be considered as guaranteed.
1- Brief About Gpic
Page 1
2- What is Methanol?
Page 2
3- Msds
Page 3
4- Gpic’s Products Handling & Export Facility
Page 8
5- Gpic Rules & Requirements
Page 9
6- Safety & Emergency Response
Page 10
7- Glossary
Page 13
Contents
DISCLAIMER MESSAGE The guidelines illustrated in this book are a summary of practices that are proven to be appropriate and suitable for the handling, transport and storage of ammonia and GPIC shall not be liable for errors, omissions or incorrect use of these guidelines. The mentioned data are based on the current state of knowledge and insights, and cannot be considered as guaranteed.
1- Brief About Gpic
Page 1
2- What is Methanol?
Page 2
3- Msds
Page 3
4- Gpic’s Products Handling & Export Facility
Page 8
5- Gpic Rules & Requirements
Page 9
6- Safety & Emergency Response
Page 10
7- Glossary
Page 13
1- Brief about GPIC Gulf Petrochemical Industries Company (GPIC) was formed in December 1979, as an equal partnership between the governments of Bahrain, Saudi Arabia and Kuwait. A site of 600,000 square metres was successfully reclaimed from the sea to house GPIC’s first petrochemical plant, namely ammonia and methanol, with production capacities of 1,000 tonnes per day of each product. The production of ammonia was commenced on 19 June 1985 and methanol production on 2 July 1985, with the first product being exported in August 1985. In December 1989, both Ammonia and Methanol plants were expanded (debottlenecked) to capacities of 1,200 tonnes per day for each product. In September 1995, GPIC signed a contract with Mitsubishi Heavy Industries Ltd. (MHI) Japan for the design and construction of a Granular Urea Plant with a capacity of 1,700 tonnes per day. This project was successfully completed in record time and the Urea plant was commissioned successfully and production was achieved on 7 January 1998.
1
The challenges of climate change have always been taken seriously at GPIC, and in order to manage our greenhouse gas emissions we commissioned the Middle East’s first Carbon Dioxide Recovery plant in 2009. The unit designed by MHI has a design capacity to capture 450 MT of carbon dioxide per day from the Methanol plant reformer stack flue gases and recycle back. GPIC export facilities for ammonia and methanol are situated at the Bahrain Petroleum Company (BAPCO) wharf in Sitra. Two ammonia and two methanol hydraulic loading arms are utilised to load the liquid product into tanker ships. The export lines stretch over a length of around 4 km from the GPIC complex.
2- What is Methanol? Methanol is a hydrocarbon that is derived from natural gas, comprised of carbon, hydrogen and oxygen. Its chemical formula is CH3OH. Methanol is a colourless alcohol and a neutral and flammable liquid. It is miscible with water, alcohols, esters and most other organic solvents. GPIC produces Methanol using a catalytic process with natural gas and steam as the feedstock. The natural gas is catalytically reformed to carbon oxides and hydrogen. The resulting synthesis gas mixture is circulated under pressure and moderate temperature in the presence of a metallic catalyst and converted to crude methanol. The crude methanol is distilled to yield commercial chemical grade methanol.
antifreeze, fuels, waste water treatment and biodiesel production. Other common names for methanol include methyl alcohol, methyl hydrate, wood spirit, wood alcohol and methyl hydroxide. The awareness of personnel involved in exporting, transporting and storing of methanol is a prime factor with a view to ensuring that the product is handled, transported and stored, incorporating the measures for preserving its quality. This book highlights important guidelines, characteristics and precautions necessary to ensure proper care is taken to protect the product and the personnel. Terminal safety, security and environmental guidelines are also addressed in the book for the benefit of all personnel involved.
Methanol is the main element for many chemicals and products. Other uses include windshield washer,
H H
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O H 2
1- Brief about GPIC Gulf Petrochemical Industries Company (GPIC) was formed in December 1979, as an equal partnership between the governments of Bahrain, Saudi Arabia and Kuwait. A site of 600,000 square metres was successfully reclaimed from the sea to house GPIC’s first petrochemical plant, namely ammonia and methanol, with production capacities of 1,000 tonnes per day of each product. The production of ammonia was commenced on 19 June 1985 and methanol production on 2 July 1985, with the first product being exported in August 1985. In December 1989, both Ammonia and Methanol plants were expanded (debottlenecked) to capacities of 1,200 tonnes per day for each product. In September 1995, GPIC signed a contract with Mitsubishi Heavy Industries Ltd. (MHI) Japan for the design and construction of a Granular Urea Plant with a capacity of 1,700 tonnes per day. This project was successfully completed in record time and the Urea plant was commissioned successfully and production was achieved on 7 January 1998.
1
The challenges of climate change have always been taken seriously at GPIC, and in order to manage our greenhouse gas emissions we commissioned the Middle East’s first Carbon Dioxide Recovery plant in 2009. The unit designed by MHI has a design capacity to capture 450 MT of carbon dioxide per day from the Methanol plant reformer stack flue gases and recycle back. GPIC export facilities for ammonia and methanol are situated at the Bahrain Petroleum Company (BAPCO) wharf in Sitra. Two ammonia and two methanol hydraulic loading arms are utilised to load the liquid product into tanker ships. The export lines stretch over a length of around 4 km from the GPIC complex.
2- What is Methanol? Methanol is a hydrocarbon that is derived from natural gas, comprised of carbon, hydrogen and oxygen. Its chemical formula is CH3OH. Methanol is a colourless alcohol and a neutral and flammable liquid. It is miscible with water, alcohols, esters and most other organic solvents. GPIC produces Methanol using a catalytic process with natural gas and steam as the feedstock. The natural gas is catalytically reformed to carbon oxides and hydrogen. The resulting synthesis gas mixture is circulated under pressure and moderate temperature in the presence of a metallic catalyst and converted to crude methanol. The crude methanol is distilled to yield commercial chemical grade methanol.
antifreeze, fuels, waste water treatment and biodiesel production. Other common names for methanol include methyl alcohol, methyl hydrate, wood spirit, wood alcohol and methyl hydroxide. The awareness of personnel involved in exporting, transporting and storing of methanol is a prime factor with a view to ensuring that the product is handled, transported and stored, incorporating the measures for preserving its quality. This book highlights important guidelines, characteristics and precautions necessary to ensure proper care is taken to protect the product and the personnel. Terminal safety, security and environmental guidelines are also addressed in the book for the benefit of all personnel involved.
Methanol is the main element for many chemicals and products. Other uses include windshield washer,
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NFPA Ratings Potential Acute Health Effects:
3- MSDS
decompose at high temperatures forming carbon monoxide and formaldehyde. Vapours are heavier than air and may travel to a source of ignition and flash back. Vapours can spread along the ground and collect in low or confined areas. Health = 1; Fire = 3; Reactivity = 0 May be fatal or cause blindness if swallowed. Vapour harmful. Flammable liquid and vapour. Harmful if swallowed, inhaled, or absorbed through the skin. Causes eye, skin, and respiratory tract irritation. May cause central nervous system depression. Cannot be made nonpoisonous.
The material safety data sheet (MSDS) provides the first insight and quick reference for personnel dealing Label directly with the product.
METHANOL Material Safety Data Sheet Section Chemical andIdentification Company Identification Section 1.1. Chemical ProductProduct and Company Product Name: Methanol GHS Product Identifier: Methanol
Synonym: Carbinol; Methyl alcohol; Methyl hydroxide; Wood alcohol; Monohydroxymethane; Wood naptha; Wood spirits; Columbian spirits; Methanol. Chemical Name: Methanol Chemical Formula: CH3OH !
Contact Information: Gulf Petrochemical Industries Company 51, Road 1401 Um Al-Baydh 614 Sitra, Kingdom of Bahrain P.O. Box : 26730 Email: SSS@gpic.net In Case of Emergency: +973 17 731777
Section 2. Composition and Information on Ingredients Section 2. Composition and Information on Ingredients Composition Name: Methanol
CAS # 67-56-1
% by Weight >99%
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Section 3. Hazards Identification
Section 3. Hazards Identification Section 3. Hazards Identification Emergency Section 3. Hazards Identification Emergency Section 3. Hazards Identification Overview: Emergency Section 3. Hazards Identification Overview: Emergency Overview: Classification: Flammable Liquid Category 1 Emergency Classification: Flammable Liquid Category 1 Overview: Hazard DANGER! Liquid Category 1 Classification: Flammable Overview: Hazard DANGER! Classification: Flammable flammable Liquid Category 1and vapour. Fatal if swallowed. Communication: Extremely liquid 1 Hazard DANGER! Classification: Flammable Liquid Category Communication: Extremely flammable liquid and vapour. Fatal if swallowed. Hazard DANGER! May damage fertility liquid for the and Communication: Extremely flammable andunborn vapour.child Fatal(fetotoxic if swallowed. Hazard DANGER! May damage fertility for the and Communication: Extremely flammable liquid andunborn vapour.child Fatal(fetotoxic if swallowed. teratogenic effects). May damage fertility liquid for the and Communication: Extremely flammable andunborn vapour.child Fatal(fetotoxic if swallowed. teratogenic effects). May damage fertilityto for theand unborn child (fetotoxic and teratogenic effects). May cause damage eyes centralchild nervous system if May damage fertility for the unborn (fetotoxic and May cause damage to eyes and central nervous system if teratogenic effects). ingested or inhaled. May cause damage to eyes and central nervous system if teratogenic effects). ingested or inhaled. May cause damagewith to eyes and central nervous system if Hazards: Colourless a mild characteristic alcohol odour ingested or liquid, inhaled. May cause damage to eyes and central nervous system if Hazards: Colourless ingested or liquid, inhaled.with a mild characteristic alcohol odour when pure. Hazards: Colourless liquid, ingested or Hygroscopic. inhaled.with a mild characteristic alcohol odour when pure. Hygroscopic. Hazards: Colourless liquid, with a mild characteristic alcohol odour Flammability Liquidpure. and vapour methanol burns with a clean, clear odour flame when Hygroscopic. Hazards: Colourless liquid, with a mild characteristic alcohol Flammability Liquidpure. and vapour methanol burns with a clean, clear flame when Hygroscopic. whichpure. is almost invisible in daylight or a light blueclear flame.flame Can Flammability Liquid and vapour methanol burns with a clean, when Hygroscopic. which is almost invisible in daylight or a light blueclear flame.flame Can Flammability Liquid and vapour methanol burns with a clean, which is almost invisible in daylight or a light blueclear flame. Can decompose at high temperatures carbon monoxide Flammability Liquid and vapour methanol burnsforming with a clean, flame decompose at high temperatures forming carbon monoxide which is almost invisible in daylight or a light blue flame. Can and formaldehyde. decompose at high temperatures forming carbon monoxide which is almost invisible in daylight or a light blue flame. Can and formaldehyde. decompose at high temperatures forming carbon monoxide Vapours are at heavier than air and forming may travel to a monoxide source of and formaldehyde. decompose high temperatures carbon Vapours are heavier than air and may travel to a source of and formaldehyde. ignition and flash back. Vapours can spread Vapours are heavier than air and may travel to a along sourcethe of and formaldehyde. ignition and flash back. Vapours can spread Vapours arecollect heavier than and may travel to a along sourcethe of ground and low orair confined areas. ignition and flash inback. Vapours can spread Vapours arecollect heavier than and may travel to a along sourcethe of ground and inback. low orair confined areas. ignition and flash Vapours can spread along the ground collect low or Vapours confined areas. NFPA Ratings Health =and 1; Fire = 3;in Reactivity =0 ignition and flash back. can spread along the NFPA Ratings Health =and 1; Fire = 3;in Reactivity =0 ground collect low or confined areas. Potential May be= 1; fatal or blindness ifareas. swallowed. Vapour NFPA Ratings Acute ground Health Fire = 3;cause Reactivity =0 collect in low or confined Potential Acute May be=and fatal or blindness swallowed. Vapour NFPA Fire = 3;cause Reactivity = 0and if HealthRatings Effects:Acute Health harmful. Flammable liquid Harmful if Potential May be= 1; fatal or blindness swallowed. Vapour NFPA 1; Fire = 3;cause Reactivity = 0and ifvapour. HealthRatings Effects:Acute Health harmful. Flammable liquid vapour. Harmful if Potential May be fatal or cause blindness if swallowed. Vapour swallowed, inhaled, or absorbed through the skin. Causes Health Effects:Acute May harmful. Flammable liquid and vapour. Harmful if Potential be fatal or cause blindness if swallowed. Vapour swallowed, inhaled, or absorbed through the skin. Causes Health Effects: harmful. Flammable liquid and vapour. Harmful if eye, skin, and respiratory tract irritation. May cause central swallowed, inhaled, or absorbed through the skin. Causes Health Effects: harmful. Flammable liquid and vapour. Harmful if eye, skin, and respiratory tract irritation. May cause Causes central swallowed, inhaled, or absorbed through the skin. eye, skin, system and respiratory tract irritation. cause central nervous depression. Cannot May be skin. madeCauses nonswallowed, inhaled, or absorbed through the nervous system depression. Cannot May be cause madecentral noneye, skin, and respiratory tract irritation. poisonous. nervous depression. Cannot May be cause madecentral noneye, skin, system and respiratory tract irritation. poisonous. nervous system depression. Cannot be made nonLabel poisonous. nervous system depression. Cannot be made nonLabel poisonous. Label poisonous. Label Label
3
Potential Chronic Health Effects: Potential Chronic Health Effects: 1- Carcinogenic Not available. Potential Chronic Health Effects: 1- Carcinogenic Not available. Potential Chronic Health Effects: 1- Effects: Carcinogenic Not available. Potential Chronic Health Effects: 2- Effects: Mutagenic Not available. available. 1Carcinogenic Not Effects: 1Not available. 2- Carcinogenic Mutagenic 2- Effects: Mutagenic Not available. Effects: 3Teratogenic Not available. 2- Mutagenic Effects: 2Not available. 3- Mutagenic Teratogenic Effects: 3- Effects: Teratogenic Not available. Effects: 4- Teratogenic Developmental Not Not available. available. 3Effects:
Potential Chronic Health Effects: 1- Carcinogenic Not available. Effects: 2- Mutagenic Not available. Effects: 3- Teratogenic Not available. Effects: 4- Developmental Not available. Toxicity: Health Hazards: Avoid contact with eyes, skin and clothing, Wash thoroughly after handling. Physical Hazards: Not available. Physical Form: Liquid. Appearance: Colourless liquid, Flash Point: 12!, 53.6". Odour: Alcohol-Like, weak odour. Potential Health Effects:
Section 4. First Aid Measures
Section 4. First Aid Measures Section 4. First Aid Measures Eye Contact: In case of contact, immediately flush eyes with plenty of water Section 4. First Aid Measures Eye Contact: In of contact, immediately flush eyes with plenty of water forcase at least 15 minutes. Get medical aid. Eye Contact: In of contact, immediately flush eyes with plenty of water forcase at least 15 minutes. Get medical aid. Skin Contact: In case of 15 contact, immediately flush for at least minutes. Get medical aid.skin with plenty of water Skin Contact: In case of contact, immediately flush skin with plenty of water forcase at least 15 minutes while removing contaminated clothing Skin Contact: In of contact, immediately flush skin with plenty of water for least 15 minutes removing contaminated and at shoes. Get medical while aid immediately. Wash clothingclothing before for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid immediately. Wash clothing before reuse. and shoes. Get medical aid immediately. Wash clothing before reuse. Inhalation: If inhaled remove to fresh air. If not breathing, give artificial reuse. Inhalation: If inhaled remove to fresh air. If not breathing, give artificial respiration. If breathing is air. difficult, give oxygen. give Get artificial medical Inhalation: If inhaled remove to fresh If not breathing, respiration. If breathing is difficult, give oxygen. Get medical aid. respiration. If breathing is difficult, give oxygen. Get medical aid. Notes to aid. Acute exposure to methanol, either through ingestion or Notes to Acute exposure to methanol, either can through or Physician: breathing high airborne concentrations result ingestion in symptoms Notes to Acute exposure to methanol, either can through ingestion or Physician: breathing high airborne concentrations resultexposure. in symptoms appearing between 40 minutes and 72 hours after Physician: breathing high airborne concentrations can result in symptoms appearing between 40 are minutes andlimited 72 hours after exposure. Symptoms and signs usually to the Central Nervous appearing 40 are minutes andlimited 72 hours after exposure. Symptomsbetween and signs usually to the Central Nervous System (CNS), gastrointestinal Because of the Symptoms and eyes signs and are usually limited totract. the Central Nervous System (CNS), eyes and gastrointestinal tract. Because the initial CNS’s effects ofgastrointestinal headache, vertigo, lethargyof System (CNS), eyes and tract. Because of and the initial CNS’s effects of headache, vertigo, lethargy and confusion, thereeffects may beofan headache, impression vertigo, of ethanollethargy intoxication. initial CNS’s and confusion, theredecreased may be an impression of ethanol are intoxication. Blurred vision, acuity and photophobia common confusion, theredecreased may be an impression of ethanol are intoxication. Blurred vision, acuity and photophobia common complaints. Blurred vision, decreased acuity and photophobia are common complaints. Treatment with ipecac or lavage is indicated in any patient complaints. Treatment or lavage is indicated in any patient presenting with withinipecac two hours of ingestion. A profound metabolic Treatment with or lavage is indicated in any patient presenting withinipecac twosevere hours of ingestion. A profound metabolic acidosis occurs in poisoning and serum bicarbonate presenting within two hours of ingestion. A profound metabolic acidosisareoccurs inaccurate severe poisoning and serum than bicarbonate levels more measure of severity serum acidosis severe poisoning and serum than bicarbonate levels areoccurs more in accurate measure methanol levels. Treatment protocols of areseverity availablethan fromserum most levels are more accurate measure of severity methanol levels. Treatment protocols are available fromserum most major hospitals and earlyprotocols collaboration with appropriate methanol levels. Treatment are available from most major hospitals and early collaboration with appropriate hospitals is recommended. major hospitals and early collaboration with appropriate hospitals is recommended. Effects may be delayed. hospitals is recommended. Effects may be delayed. Antidote: Ethanol significantly decreases the toxicity of methanol because Effects may be delayed. Antidote: Ethanol significantly the toxicity of methanol because it competes for the decreases same metabolic enzymes, and has been Antidote: Ethanol significantly the toxicity of methanol because it competes for the decreases same metabolic enzymes, and has been used to treat methanol poisoning. it competes for the same metabolic enzymes, and has been used to treat methanol poisoning. ! used to treat methanol poisoning. ! !
Section Fighting Measures Section 5. 5. FireFire Fighting Measures General Information:
•
•
As in any fire, wear a self-contained breathing apparatus in pressure-demand. MSHA/NIOSH (approved or equivalent), and full protective gear during a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to keep fire-exposed containers cool. Water may be ineffective. Material is lighter than water and fire may be spread by the use of water.
General • Measures As in any fire, wear a self-contained breathing apparatus Section 5. Fire Fighting in Information: MSHA/NIOSH (approved or General • Aspressure-demand. in any fire, wear a self-contained breathing apparatus equivalent), and full protective gear during a (approved fire, irritatingor Information: in pressure-demand. MSHA/NIOSH and highly toxic gases may be generated by thermal equivalent), and full protective gear during a fire, irritating decomposition or combustion. and highly toxic gases may be generated by thermal • Use water spray to keep fire-exposed containers cool. decomposition or combustion. Water may be ineffective. Material is lighter than water • Use water spray to keep fire-exposed containers cool. and fire may be spread by the use of water. Water may be ineffective. Material is lighter than water • Vapours are heavier than air and may travel to a source of and fire may be spread by the use of water. ignition and back. can travel spread theof • Vapours areflash heavier thanVapours air and may to along a source ground and collect low or Vapours confined can areas. ignition and flashinback. spread along the Flammable Properties ground and collect in low or confined areas. Flammability of Flammable Flammable Properties the Product: Flammability of Flammable o o Auto-Ignition 455 oC (851.00 oF) the Product: o o Temperature: Auto-Ignition 455 C (851.00 F) o o Flash Points: 12 oC (53.60 oF) Temperature: o 6.0 vol o%, upper 31.00 vol% Flammable Lower Flash Points: 12 C (53.60 F) Limits: Flammable Lower 6.0 vol %, upper 31.00 vol% Products of These products are carbon oxides (CO, CO22), and water (H22O). Limits: Combustion: Products of These products are carbon oxides (CO, CO2), and water (H2O). Fire Fighting • For small fires, use dry chemical, carbon dioxide, water Combustion: Media and or alcohol-resistant Fire Fighting • spray For small fires, use dry foam. chemical, carbon dioxide, water Instructions: • General synthetic foam. foams or protein foams may Media and spray orpurpose alcohol-resistant work, but much less effectively. Instructions: • General purpose synthetic foams or protein foams may • Use water spray less to keep fire-exposed containers cool. work, but much effectively. may bespray ineffective. is lighter than water • Water Use water to keep Material fire-exposed containers cool. and fire may by the Material use of water. Water may be be spread ineffective. is lighter than water Special • Methanol vapours may burn with an invisible flame. and firea may spread monoxide, by the use of water. dioxide and • During fire,becarbon carbon Remarks Special on Fire • Methanol vapours may burn with an invisible flame. irritating and toxic gases such as formaldehyde may be Hazards: • During a fire, carbon monoxide, carbon dioxide and Remarks on Fire generated. irritating and toxic gases such as formaldehyde may be Hazards: • Vapours can accumulate in confined spaces resulting in a generated. toxicity and flammability hazard. • Vapours can accumulate in confined spaces resulting in a Special • Close containers may rupture violently and suddenly, toxicity and flammability hazard. releasing large quantities of methanol when exposed to Remarks Special on • Close containers may rupture violently and suddenly, fire or excessive heat for a sufficient period of time Explosion releasing quantities methanol exposed Remarks on • Vapours arelarge slightly heavier of than air and when may travel longto Hazards: fire or excessive heat for a sufficient period of time Explosion distances toward source of ignition. Not available. • Vapours are slightly heavier than air and may travel long Hazards: Unusual Fire Not available. distances toward source of ignition. Not available. and Explosion Unusual Fire Not available. Hazards: and Explosion Hazards:
! Section 6. Accidental Release Measures
Section 6. Accidental Release Measures ! Section 6. AccidentalUse Release Measures General proper personal protective equipment as indicated in General Use proper information: Section 8. personal protective equipment as indicated in information: Section 8. water spray to disperse the gas/vapour. Methanol is Spill/ leaks: 1- Use a water use of waterMethanol to prevent Spill/ leaks: 1- Use waterpollutant. spray to Minimize disperse the gas/vapour. is pollution. aenvironment water pollutant. Minimize the use of water to prevent 2- environment Remove all sources of ignition. pollution. 3- Remove Absorb allspill using an absorbent, non-combustible 2sources of ignition. 3- Absorb using absorbent, non-combustible material spill such as earth,an sand, or vermiculite. Do not use combustible material suchmaterials as earth, such sand,asorsawdust. vermiculite. Do not use 4- combustible Use spark-proof tools. Provide ventilation. A vapour materials such as sawdust. suppressing foamtools. may be used toventilation. reduce vapours. Water 4- Use spark-proof Provide A vapour spray may reduce vapour but may not prevent ignition in suppressing foam may be used to reduce vapours. Water spray may reduce vapour but may not prevent ignition in closed spaces. ! closed spaces. !
Section 7. Handling and Storage
Section 7. Handling and Storage Precautions for 1- No smoking or open flame in storage, use or handling areas. Handling: 2- Use explosion proof electrical equipment. Ensure proper electrical grounding procedures are in place. 3- Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. 4- Ground and bond containers when transferring material. 5- Use spark-proof tools and explosion proof equipment. 6- Avoid contact with eyes, skin, and clothing. 7- Empty containers retain product residue, (liquid and/or vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale. 8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation. 9- Keep away from heat, sparks and flame. Avoid use in confined spaces. Storage: 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition.
Storage:
!
7- Empty containers retain product residue, (liquid and/or vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale. 8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation. 9- Keep away from heat, sparks and flame. Avoid use in confined spaces. 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition. 2- Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area. Keep containers tightly closed. 3- Tanks must be grounded, vented, and should have vapour emission controls. 4- Tanks must be diked as per NFPA or API Standards. 5- A flammable mixture of methanol vapour and air is possible inside a storage tank or transportation tank, and handlers should take appropriate precautions to reduce the risk of ignition. Handlers must eliminate ignition sources or purge the tank with an inert gas such as nitrogen. 6- All equipment must be grounded / bonded when transferring product in order to avoid static discharge from the equipment, and subsequent possible fire. 7- Avoid storage with incompatible materials. Anhydrous methanol is not corrosive to most metals at ambient temperatures except lead, nickel, monel, cast iron and high silicon iron. Coatings of copper (or Copper alloys), zinc (including galvanized steel), or aluminium are unsuitable for storage. These materials may be attacked slowly by the methanol. 8- Storage tanks of welded construction are normally satisfactory. 9- Plastics are suitable only for short term storage of methanol.
Section 8. Exposure Controls/Personal Protection
Section 8. Exposure Controls/Personal Protection Section 8. Exposure Controls/Personal Protection Engineering Use explosion- proof ventilation equipment in confined areas. Engineering explosion- proof ventilation equipment in confined areas. Section 8. ExposureUse Controls/Personal Protection Controls: Facilities storing or utilising this material should be equipped Controls: storingproof orProtection utilising this equipment material should be equipped Engineering Use explosionventilation in confined areas. Section 8. ExposureFacilities Controls/Personal with an eyewash facility and a safety shower. Use adequate Controls: Facilities storingproof or utilising material should be equipped with an eyewash facility and this a safety shower. Use adequate Engineering Use explosionventilation equipment areas. general or local exhaust ventilation toin confined keep airborne general or local exhaust to keep airborne with an eyewash facility and this aventilation safety shower. Use adequate Controls: Facilities storing or utilising material should be equipped concentrations below the permissible exposure limits. concentrations below the permissible exposure limits. general or localfacility exhaust to keep airborne with an the eyewash and aventilation safety shower. Respiratory Follow OSHA respirator regulations foundUse in adequate 29 CFR Respiratory Follow OSHA regulations found 29 CFR concentrations belowrespirator the permissible exposure limits. general the or European local exhaust keepin airborne Protection 1910.134 or Standardventilation EN 149. Usetoa NIOSH/MSHA or Protection 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or Respiratory Follow the OSHA respirator regulations found in 29 CFR concentrations belowEN the 149 permissible exposure limits. European Standard approved respirator if exposure Protection 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure Respiratory Follow are the exceeded OSHA respirator regulations found in 29 CFR limits or if irritation or other symptoms are limits areorStandard exceeded or if irritation or respirator other symptoms are European 149 approved if exposure Protection 1910.134 EuropeanEN Standard EN 149. Use a NIOSH/MSHA or experienced. experienced. limits are Standard exceeded EN or 149 if irritation or respirator other symptoms are European approved if exposure NIOSH/OSHA recommendations for methanol concentrations in NIOSH/OSHA recommendations for methanol concentrations in experienced. limits are exceeded or if irritation or other symptoms are air: air: NIOSH/OSHA recommendations for methanol concentrations in experienced. 1- Up to 2000 ppm: supplied air respirator. 1ppm: supplied air respirator. air: NIOSH/OSHA recommendations forair methanol concentrations 2- Up Up to to2000 5000 ppm: supplied respirator operated in in a 2- Up to to2000 5000ppm: ppm: supplied respirator operated in a supplied air air respirator. flow mode. air: 1- continuous continuous flow mode. 2- Up to 6000 5000ppm: ppm: supplied air respirator operated in a 3to supplied air respirator with a tight-fitting 1to supplied air 3- Up Up to 2000 6000 ppm: ppm: supplied air respirator. respiratorflow withmode; a tight-fitting continuous flow mode. in a continuous or in Full 2- face Up topiece 5000operated ppm: supplied air respirator operated a operated in a continuous or Full Full 3- face Up topiece 6000 ppm: supplied airbreathing respiratorflow withmode; a tight-fitting face piece self-contained apparatus or continuous flow mode. face piece self-contained breathing apparatus or Full face piece operated in a continuous flow mode; or Full facetopiece supplied air respirator. 3- Up 6000 ppm: supplied air respirator with a tight-fitting piece air respirator. piecesupplied self-contained breathing apparatus or Full 4- face Cartridge respirators NOT recommended. face piecetype operated in a are continuous flow mode; or Full Cartridge type respirators are NOT faceinto piece supplied air respirator. Emergency or Planned4-entry unknown concentrations orrecommended. IDLH conditions: faceinto piece self-contained breathing apparatus or Full Emergency or Planned4-entry unknown concentrations or IDLH conditions: Cartridge typemust respirators areby NOT recommended. Respirator: Respirator a qualified person and be face selection piece supplied be air done respirator. Respirator: Respirator selection must be done by aor qualified person and be Emergency or Planned entry into unknown concentrations IDLH conditions: based a risk assessment of are the NOT workrecommended. activities. Respirators 4- upon Cartridge type respirators based uponselection a risk assessment of the activities. Respirators Respirator: Respirator must be done bywork aor qualified person and be Emergency or Planned unknown concentrations IDLH conditions: mustentry be fitinto tested and users must be clean shaven where the based upon a risk assessment of the work activities. Respirators must be fitselection tested and users must be clean shaven where the Respirator: Respirator must beExposure done by amust qualified person be respirator seals to the face. be kept at orand below respirator toassessment the must kept Respirators atwhere or below must be fitseals tested and face. usersExposure must cleanbe shaven the basedapplicable upon a risk of thebe work the exposure limits and activities. the maximum use the applicable exposure limits and the maximum use respirator seals to the face. Exposure must be kept at or below must be fit tested users must shaven where the concentration of theand respirator must be notclean be exceeded. concentration of to the respirator must not exceeded. the applicable exposure limits andbe the maximum use the face. Exposure be kept at or below Skin Protection: respirator Wear butylseals rubber gloves, apron, and/ormust clothing. Skin Protection: Wear butyl rubber gloves, apron, and/or clothing. concentration of the respirator must not be exceeded. the applicable exposuresplash limitsgoggles and the Eye and Face Face shield and chemical whenmaximum transferringuse is Skin Protection: Wear butyl gloves, apron, and/or clothing. Eye and Face Face shieldrubber and chemical splash goggles when transferring is concentration of the respirator must not Protection taking place. Contact lenses should notbe beexceeded. worn when working Protection taking place. Contact lenses should not be worn when working Eye and Face Face shield and chemical splash goggles when transferring is Skin Protection: with Wearmethanol. butyl rubber gloves, apron, and/or clothing. Protection taking place.and Contact lenses should not be when worn transferring when working Eye and Face with Facemethanol. shield chemical splash goggles is Footwear Chemical resistant and as specified by the workplace Footwear Chemical resistant andlenses as specified by thebeworkplace with methanol. Protection taking place. not worn working Other Eyewash and Contact showers shouldshould be located near workwhen areas. Other Eyewash and showers should be located near work areas. Footwear Chemical resistant and as specified by the workplace with methanol. ! Eyewash showers be located work areas. ! Other Footwear Chemical and resistant andshould as specified by thenear workplace ! Other Eyewash and showers should be located near work areas. !
4
NFPA Ratings Potential Acute Health Effects:
3- MSDS
decompose at high temperatures forming carbon monoxide and formaldehyde. Vapours are heavier than air and may travel to a source of ignition and flash back. Vapours can spread along the ground and collect in low or confined areas. Health = 1; Fire = 3; Reactivity = 0 May be fatal or cause blindness if swallowed. Vapour harmful. Flammable liquid and vapour. Harmful if swallowed, inhaled, or absorbed through the skin. Causes eye, skin, and respiratory tract irritation. May cause central nervous system depression. Cannot be made nonpoisonous.
The material safety data sheet (MSDS) provides the first insight and quick reference for personnel dealing Label directly with the product.
METHANOL Material Safety Data Sheet Section Chemical andIdentification Company Identification Section 1.1. Chemical ProductProduct and Company Product Name: Methanol GHS Product Identifier: Methanol
Synonym: Carbinol; Methyl alcohol; Methyl hydroxide; Wood alcohol; Monohydroxymethane; Wood naptha; Wood spirits; Columbian spirits; Methanol. Chemical Name: Methanol Chemical Formula: CH3OH !
Contact Information: Gulf Petrochemical Industries Company 51, Road 1401 Um Al-Baydh 614 Sitra, Kingdom of Bahrain P.O. Box : 26730 Email: SSS@gpic.net In Case of Emergency: +973 17 731777
Section 2. Composition and Information on Ingredients Section 2. Composition and Information on Ingredients Composition Name: Methanol
CAS # 67-56-1
% by Weight >99%
!
Section 3. Hazards Identification
Section 3. Hazards Identification Section 3. Hazards Identification Emergency Section 3. Hazards Identification Emergency Section 3. Hazards Identification Overview: Emergency Section 3. Hazards Identification Overview: Emergency Overview: Classification: Flammable Liquid Category 1 Emergency Classification: Flammable Liquid Category 1 Overview: Hazard DANGER! Liquid Category 1 Classification: Flammable Overview: Hazard DANGER! Classification: Flammable flammable Liquid Category 1and vapour. Fatal if swallowed. Communication: Extremely liquid 1 Hazard DANGER! Classification: Flammable Liquid Category Communication: Extremely flammable liquid and vapour. Fatal if swallowed. Hazard DANGER! May damage fertility liquid for the and Communication: Extremely flammable andunborn vapour.child Fatal(fetotoxic if swallowed. Hazard DANGER! May damage fertility for the and Communication: Extremely flammable liquid andunborn vapour.child Fatal(fetotoxic if swallowed. teratogenic effects). May damage fertility liquid for the and Communication: Extremely flammable andunborn vapour.child Fatal(fetotoxic if swallowed. teratogenic effects). May damage fertilityto for theand unborn child (fetotoxic and teratogenic effects). May cause damage eyes centralchild nervous system if May damage fertility for the unborn (fetotoxic and May cause damage to eyes and central nervous system if teratogenic effects). ingested or inhaled. May cause damage to eyes and central nervous system if teratogenic effects). ingested or inhaled. May cause damagewith to eyes and central nervous system if Hazards: Colourless a mild characteristic alcohol odour ingested or liquid, inhaled. May cause damage to eyes and central nervous system if Hazards: Colourless ingested or liquid, inhaled.with a mild characteristic alcohol odour when pure. Hazards: Colourless liquid, ingested or Hygroscopic. inhaled.with a mild characteristic alcohol odour when pure. Hygroscopic. Hazards: Colourless liquid, with a mild characteristic alcohol odour Flammability Liquidpure. and vapour methanol burns with a clean, clear odour flame when Hygroscopic. Hazards: Colourless liquid, with a mild characteristic alcohol Flammability Liquidpure. and vapour methanol burns with a clean, clear flame when Hygroscopic. whichpure. is almost invisible in daylight or a light blueclear flame.flame Can Flammability Liquid and vapour methanol burns with a clean, when Hygroscopic. which is almost invisible in daylight or a light blueclear flame.flame Can Flammability Liquid and vapour methanol burns with a clean, which is almost invisible in daylight or a light blueclear flame. Can decompose at high temperatures carbon monoxide Flammability Liquid and vapour methanol burnsforming with a clean, flame decompose at high temperatures forming carbon monoxide which is almost invisible in daylight or a light blue flame. Can and formaldehyde. decompose at high temperatures forming carbon monoxide which is almost invisible in daylight or a light blue flame. Can and formaldehyde. decompose at high temperatures forming carbon monoxide Vapours are at heavier than air and forming may travel to a monoxide source of and formaldehyde. decompose high temperatures carbon Vapours are heavier than air and may travel to a source of and formaldehyde. ignition and flash back. Vapours can spread Vapours are heavier than air and may travel to a along sourcethe of and formaldehyde. ignition and flash back. Vapours can spread Vapours arecollect heavier than and may travel to a along sourcethe of ground and low orair confined areas. ignition and flash inback. Vapours can spread Vapours arecollect heavier than and may travel to a along sourcethe of ground and inback. low orair confined areas. ignition and flash Vapours can spread along the ground collect low or Vapours confined areas. NFPA Ratings Health =and 1; Fire = 3;in Reactivity =0 ignition and flash back. can spread along the NFPA Ratings Health =and 1; Fire = 3;in Reactivity =0 ground collect low or confined areas. Potential May be= 1; fatal or blindness ifareas. swallowed. Vapour NFPA Ratings Acute ground Health Fire = 3;cause Reactivity =0 collect in low or confined Potential Acute May be=and fatal or blindness swallowed. Vapour NFPA Fire = 3;cause Reactivity = 0and if HealthRatings Effects:Acute Health harmful. Flammable liquid Harmful if Potential May be= 1; fatal or blindness swallowed. Vapour NFPA 1; Fire = 3;cause Reactivity = 0and ifvapour. HealthRatings Effects:Acute Health harmful. Flammable liquid vapour. Harmful if Potential May be fatal or cause blindness if swallowed. Vapour swallowed, inhaled, or absorbed through the skin. Causes Health Effects:Acute May harmful. Flammable liquid and vapour. Harmful if Potential be fatal or cause blindness if swallowed. Vapour swallowed, inhaled, or absorbed through the skin. Causes Health Effects: harmful. Flammable liquid and vapour. Harmful if eye, skin, and respiratory tract irritation. May cause central swallowed, inhaled, or absorbed through the skin. Causes Health Effects: harmful. Flammable liquid and vapour. Harmful if eye, skin, and respiratory tract irritation. May cause Causes central swallowed, inhaled, or absorbed through the skin. eye, skin, system and respiratory tract irritation. cause central nervous depression. Cannot May be skin. madeCauses nonswallowed, inhaled, or absorbed through the nervous system depression. Cannot May be cause madecentral noneye, skin, and respiratory tract irritation. poisonous. nervous depression. Cannot May be cause madecentral noneye, skin, system and respiratory tract irritation. poisonous. nervous system depression. Cannot be made nonLabel poisonous. nervous system depression. Cannot be made nonLabel poisonous. Label poisonous. Label Label
3
Potential Chronic Health Effects: Potential Chronic Health Effects: 1- Carcinogenic Not available. Potential Chronic Health Effects: 1- Carcinogenic Not available. Potential Chronic Health Effects: 1- Effects: Carcinogenic Not available. Potential Chronic Health Effects: 2- Effects: Mutagenic Not available. available. 1Carcinogenic Not Effects: 1Not available. 2- Carcinogenic Mutagenic 2- Effects: Mutagenic Not available. Effects: 3Teratogenic Not available. 2- Mutagenic Effects: 2Not available. 3- Mutagenic Teratogenic Effects: 3- Effects: Teratogenic Not available. Effects: 4- Teratogenic Developmental Not Not available. available. 3Effects:
Potential Chronic Health Effects: 1- Carcinogenic Not available. Effects: 2- Mutagenic Not available. Effects: 3- Teratogenic Not available. Effects: 4- Developmental Not available. Toxicity: Health Hazards: Avoid contact with eyes, skin and clothing, Wash thoroughly after handling. Physical Hazards: Not available. Physical Form: Liquid. Appearance: Colourless liquid, Flash Point: 12!, 53.6". Odour: Alcohol-Like, weak odour. Potential Health Effects:
Section 4. First Aid Measures
Section 4. First Aid Measures Section 4. First Aid Measures Eye Contact: In case of contact, immediately flush eyes with plenty of water Section 4. First Aid Measures Eye Contact: In of contact, immediately flush eyes with plenty of water forcase at least 15 minutes. Get medical aid. Eye Contact: In of contact, immediately flush eyes with plenty of water forcase at least 15 minutes. Get medical aid. Skin Contact: In case of 15 contact, immediately flush for at least minutes. Get medical aid.skin with plenty of water Skin Contact: In case of contact, immediately flush skin with plenty of water forcase at least 15 minutes while removing contaminated clothing Skin Contact: In of contact, immediately flush skin with plenty of water for least 15 minutes removing contaminated and at shoes. Get medical while aid immediately. Wash clothingclothing before for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid immediately. Wash clothing before reuse. and shoes. Get medical aid immediately. Wash clothing before reuse. Inhalation: If inhaled remove to fresh air. If not breathing, give artificial reuse. Inhalation: If inhaled remove to fresh air. If not breathing, give artificial respiration. If breathing is air. difficult, give oxygen. give Get artificial medical Inhalation: If inhaled remove to fresh If not breathing, respiration. If breathing is difficult, give oxygen. Get medical aid. respiration. If breathing is difficult, give oxygen. Get medical aid. Notes to aid. Acute exposure to methanol, either through ingestion or Notes to Acute exposure to methanol, either can through or Physician: breathing high airborne concentrations result ingestion in symptoms Notes to Acute exposure to methanol, either can through ingestion or Physician: breathing high airborne concentrations resultexposure. in symptoms appearing between 40 minutes and 72 hours after Physician: breathing high airborne concentrations can result in symptoms appearing between 40 are minutes andlimited 72 hours after exposure. Symptoms and signs usually to the Central Nervous appearing 40 are minutes andlimited 72 hours after exposure. Symptomsbetween and signs usually to the Central Nervous System (CNS), gastrointestinal Because of the Symptoms and eyes signs and are usually limited totract. the Central Nervous System (CNS), eyes and gastrointestinal tract. Because the initial CNS’s effects ofgastrointestinal headache, vertigo, lethargyof System (CNS), eyes and tract. Because of and the initial CNS’s effects of headache, vertigo, lethargy and confusion, thereeffects may beofan headache, impression vertigo, of ethanollethargy intoxication. initial CNS’s and confusion, theredecreased may be an impression of ethanol are intoxication. Blurred vision, acuity and photophobia common confusion, theredecreased may be an impression of ethanol are intoxication. Blurred vision, acuity and photophobia common complaints. Blurred vision, decreased acuity and photophobia are common complaints. Treatment with ipecac or lavage is indicated in any patient complaints. Treatment or lavage is indicated in any patient presenting with withinipecac two hours of ingestion. A profound metabolic Treatment with or lavage is indicated in any patient presenting withinipecac twosevere hours of ingestion. A profound metabolic acidosis occurs in poisoning and serum bicarbonate presenting within two hours of ingestion. A profound metabolic acidosisareoccurs inaccurate severe poisoning and serum than bicarbonate levels more measure of severity serum acidosis severe poisoning and serum than bicarbonate levels areoccurs more in accurate measure methanol levels. Treatment protocols of areseverity availablethan fromserum most levels are more accurate measure of severity methanol levels. Treatment protocols are available fromserum most major hospitals and earlyprotocols collaboration with appropriate methanol levels. Treatment are available from most major hospitals and early collaboration with appropriate hospitals is recommended. major hospitals and early collaboration with appropriate hospitals is recommended. Effects may be delayed. hospitals is recommended. Effects may be delayed. Antidote: Ethanol significantly decreases the toxicity of methanol because Effects may be delayed. Antidote: Ethanol significantly the toxicity of methanol because it competes for the decreases same metabolic enzymes, and has been Antidote: Ethanol significantly the toxicity of methanol because it competes for the decreases same metabolic enzymes, and has been used to treat methanol poisoning. it competes for the same metabolic enzymes, and has been used to treat methanol poisoning. ! used to treat methanol poisoning. ! !
Section Fighting Measures Section 5. 5. FireFire Fighting Measures General Information:
•
•
As in any fire, wear a self-contained breathing apparatus in pressure-demand. MSHA/NIOSH (approved or equivalent), and full protective gear during a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to keep fire-exposed containers cool. Water may be ineffective. Material is lighter than water and fire may be spread by the use of water.
General • Measures As in any fire, wear a self-contained breathing apparatus Section 5. Fire Fighting in Information: MSHA/NIOSH (approved or General • Aspressure-demand. in any fire, wear a self-contained breathing apparatus equivalent), and full protective gear during a (approved fire, irritatingor Information: in pressure-demand. MSHA/NIOSH and highly toxic gases may be generated by thermal equivalent), and full protective gear during a fire, irritating decomposition or combustion. and highly toxic gases may be generated by thermal • Use water spray to keep fire-exposed containers cool. decomposition or combustion. Water may be ineffective. Material is lighter than water • Use water spray to keep fire-exposed containers cool. and fire may be spread by the use of water. Water may be ineffective. Material is lighter than water • Vapours are heavier than air and may travel to a source of and fire may be spread by the use of water. ignition and back. can travel spread theof • Vapours areflash heavier thanVapours air and may to along a source ground and collect low or Vapours confined can areas. ignition and flashinback. spread along the Flammable Properties ground and collect in low or confined areas. Flammability of Flammable Flammable Properties the Product: Flammability of Flammable o o Auto-Ignition 455 oC (851.00 oF) the Product: o o Temperature: Auto-Ignition 455 C (851.00 F) o o Flash Points: 12 oC (53.60 oF) Temperature: o 6.0 vol o%, upper 31.00 vol% Flammable Lower Flash Points: 12 C (53.60 F) Limits: Flammable Lower 6.0 vol %, upper 31.00 vol% Products of These products are carbon oxides (CO, CO22), and water (H22O). Limits: Combustion: Products of These products are carbon oxides (CO, CO2), and water (H2O). Fire Fighting • For small fires, use dry chemical, carbon dioxide, water Combustion: Media and or alcohol-resistant Fire Fighting • spray For small fires, use dry foam. chemical, carbon dioxide, water Instructions: • General synthetic foam. foams or protein foams may Media and spray orpurpose alcohol-resistant work, but much less effectively. Instructions: • General purpose synthetic foams or protein foams may • Use water spray less to keep fire-exposed containers cool. work, but much effectively. may bespray ineffective. is lighter than water • Water Use water to keep Material fire-exposed containers cool. and fire may by the Material use of water. Water may be be spread ineffective. is lighter than water Special • Methanol vapours may burn with an invisible flame. and firea may spread monoxide, by the use of water. dioxide and • During fire,becarbon carbon Remarks Special on Fire • Methanol vapours may burn with an invisible flame. irritating and toxic gases such as formaldehyde may be Hazards: • During a fire, carbon monoxide, carbon dioxide and Remarks on Fire generated. irritating and toxic gases such as formaldehyde may be Hazards: • Vapours can accumulate in confined spaces resulting in a generated. toxicity and flammability hazard. • Vapours can accumulate in confined spaces resulting in a Special • Close containers may rupture violently and suddenly, toxicity and flammability hazard. releasing large quantities of methanol when exposed to Remarks Special on • Close containers may rupture violently and suddenly, fire or excessive heat for a sufficient period of time Explosion releasing quantities methanol exposed Remarks on • Vapours arelarge slightly heavier of than air and when may travel longto Hazards: fire or excessive heat for a sufficient period of time Explosion distances toward source of ignition. Not available. • Vapours are slightly heavier than air and may travel long Hazards: Unusual Fire Not available. distances toward source of ignition. Not available. and Explosion Unusual Fire Not available. Hazards: and Explosion Hazards:
! Section 6. Accidental Release Measures
Section 6. Accidental Release Measures ! Section 6. AccidentalUse Release Measures General proper personal protective equipment as indicated in General Use proper information: Section 8. personal protective equipment as indicated in information: Section 8. water spray to disperse the gas/vapour. Methanol is Spill/ leaks: 1- Use a water use of waterMethanol to prevent Spill/ leaks: 1- Use waterpollutant. spray to Minimize disperse the gas/vapour. is pollution. aenvironment water pollutant. Minimize the use of water to prevent 2- environment Remove all sources of ignition. pollution. 3- Remove Absorb allspill using an absorbent, non-combustible 2sources of ignition. 3- Absorb using absorbent, non-combustible material spill such as earth,an sand, or vermiculite. Do not use combustible material suchmaterials as earth, such sand,asorsawdust. vermiculite. Do not use 4- combustible Use spark-proof tools. Provide ventilation. A vapour materials such as sawdust. suppressing foamtools. may be used toventilation. reduce vapours. Water 4- Use spark-proof Provide A vapour spray may reduce vapour but may not prevent ignition in suppressing foam may be used to reduce vapours. Water spray may reduce vapour but may not prevent ignition in closed spaces. ! closed spaces. !
Section 7. Handling and Storage
Section 7. Handling and Storage Precautions for 1- No smoking or open flame in storage, use or handling areas. Handling: 2- Use explosion proof electrical equipment. Ensure proper electrical grounding procedures are in place. 3- Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. 4- Ground and bond containers when transferring material. 5- Use spark-proof tools and explosion proof equipment. 6- Avoid contact with eyes, skin, and clothing. 7- Empty containers retain product residue, (liquid and/or vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale. 8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation. 9- Keep away from heat, sparks and flame. Avoid use in confined spaces. Storage: 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition.
Storage:
!
7- Empty containers retain product residue, (liquid and/or vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale. 8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation. 9- Keep away from heat, sparks and flame. Avoid use in confined spaces. 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition. 2- Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area. Keep containers tightly closed. 3- Tanks must be grounded, vented, and should have vapour emission controls. 4- Tanks must be diked as per NFPA or API Standards. 5- A flammable mixture of methanol vapour and air is possible inside a storage tank or transportation tank, and handlers should take appropriate precautions to reduce the risk of ignition. Handlers must eliminate ignition sources or purge the tank with an inert gas such as nitrogen. 6- All equipment must be grounded / bonded when transferring product in order to avoid static discharge from the equipment, and subsequent possible fire. 7- Avoid storage with incompatible materials. Anhydrous methanol is not corrosive to most metals at ambient temperatures except lead, nickel, monel, cast iron and high silicon iron. Coatings of copper (or Copper alloys), zinc (including galvanized steel), or aluminium are unsuitable for storage. These materials may be attacked slowly by the methanol. 8- Storage tanks of welded construction are normally satisfactory. 9- Plastics are suitable only for short term storage of methanol.
Section 8. Exposure Controls/Personal Protection
Section 8. Exposure Controls/Personal Protection Section 8. Exposure Controls/Personal Protection Engineering Use explosion- proof ventilation equipment in confined areas. Engineering explosion- proof ventilation equipment in confined areas. Section 8. ExposureUse Controls/Personal Protection Controls: Facilities storing or utilising this material should be equipped Controls: storingproof orProtection utilising this equipment material should be equipped Engineering Use explosionventilation in confined areas. Section 8. ExposureFacilities Controls/Personal with an eyewash facility and a safety shower. Use adequate Controls: Facilities storingproof or utilising material should be equipped with an eyewash facility and this a safety shower. Use adequate Engineering Use explosionventilation equipment areas. general or local exhaust ventilation toin confined keep airborne general or local exhaust to keep airborne with an eyewash facility and this aventilation safety shower. Use adequate Controls: Facilities storing or utilising material should be equipped concentrations below the permissible exposure limits. concentrations below the permissible exposure limits. general or localfacility exhaust to keep airborne with an the eyewash and aventilation safety shower. Respiratory Follow OSHA respirator regulations foundUse in adequate 29 CFR Respiratory Follow OSHA regulations found 29 CFR concentrations belowrespirator the permissible exposure limits. general the or European local exhaust keepin airborne Protection 1910.134 or Standardventilation EN 149. Usetoa NIOSH/MSHA or Protection 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or Respiratory Follow the OSHA respirator regulations found in 29 CFR concentrations belowEN the 149 permissible exposure limits. European Standard approved respirator if exposure Protection 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure Respiratory Follow are the exceeded OSHA respirator regulations found in 29 CFR limits or if irritation or other symptoms are limits areorStandard exceeded or if irritation or respirator other symptoms are European 149 approved if exposure Protection 1910.134 EuropeanEN Standard EN 149. Use a NIOSH/MSHA or experienced. experienced. limits are Standard exceeded EN or 149 if irritation or respirator other symptoms are European approved if exposure NIOSH/OSHA recommendations for methanol concentrations in NIOSH/OSHA recommendations for methanol concentrations in experienced. limits are exceeded or if irritation or other symptoms are air: air: NIOSH/OSHA recommendations for methanol concentrations in experienced. 1- Up to 2000 ppm: supplied air respirator. 1ppm: supplied air respirator. air: NIOSH/OSHA recommendations forair methanol concentrations 2- Up Up to to2000 5000 ppm: supplied respirator operated in in a 2- Up to to2000 5000ppm: ppm: supplied respirator operated in a supplied air air respirator. flow mode. air: 1- continuous continuous flow mode. 2- Up to 6000 5000ppm: ppm: supplied air respirator operated in a 3to supplied air respirator with a tight-fitting 1to supplied air 3- Up Up to 2000 6000 ppm: ppm: supplied air respirator. respiratorflow withmode; a tight-fitting continuous flow mode. in a continuous or in Full 2- face Up topiece 5000operated ppm: supplied air respirator operated a operated in a continuous or Full Full 3- face Up topiece 6000 ppm: supplied airbreathing respiratorflow withmode; a tight-fitting face piece self-contained apparatus or continuous flow mode. face piece self-contained breathing apparatus or Full face piece operated in a continuous flow mode; or Full facetopiece supplied air respirator. 3- Up 6000 ppm: supplied air respirator with a tight-fitting piece air respirator. piecesupplied self-contained breathing apparatus or Full 4- face Cartridge respirators NOT recommended. face piecetype operated in a are continuous flow mode; or Full Cartridge type respirators are NOT faceinto piece supplied air respirator. Emergency or Planned4-entry unknown concentrations orrecommended. IDLH conditions: faceinto piece self-contained breathing apparatus or Full Emergency or Planned4-entry unknown concentrations or IDLH conditions: Cartridge typemust respirators areby NOT recommended. Respirator: Respirator a qualified person and be face selection piece supplied be air done respirator. Respirator: Respirator selection must be done by aor qualified person and be Emergency or Planned entry into unknown concentrations IDLH conditions: based a risk assessment of are the NOT workrecommended. activities. Respirators 4- upon Cartridge type respirators based uponselection a risk assessment of the activities. Respirators Respirator: Respirator must be done bywork aor qualified person and be Emergency or Planned unknown concentrations IDLH conditions: mustentry be fitinto tested and users must be clean shaven where the based upon a risk assessment of the work activities. Respirators must be fitselection tested and users must be clean shaven where the Respirator: Respirator must beExposure done by amust qualified person be respirator seals to the face. be kept at orand below respirator toassessment the must kept Respirators atwhere or below must be fitseals tested and face. usersExposure must cleanbe shaven the basedapplicable upon a risk of thebe work the exposure limits and activities. the maximum use the applicable exposure limits and the maximum use respirator seals to the face. Exposure must be kept at or below must be fit tested users must shaven where the concentration of theand respirator must be notclean be exceeded. concentration of to the respirator must not exceeded. the applicable exposure limits andbe the maximum use the face. Exposure be kept at or below Skin Protection: respirator Wear butylseals rubber gloves, apron, and/ormust clothing. Skin Protection: Wear butyl rubber gloves, apron, and/or clothing. concentration of the respirator must not be exceeded. the applicable exposuresplash limitsgoggles and the Eye and Face Face shield and chemical whenmaximum transferringuse is Skin Protection: Wear butyl gloves, apron, and/or clothing. Eye and Face Face shieldrubber and chemical splash goggles when transferring is concentration of the respirator must not Protection taking place. Contact lenses should notbe beexceeded. worn when working Protection taking place. Contact lenses should not be worn when working Eye and Face Face shield and chemical splash goggles when transferring is Skin Protection: with Wearmethanol. butyl rubber gloves, apron, and/or clothing. Protection taking place.and Contact lenses should not be when worn transferring when working Eye and Face with Facemethanol. shield chemical splash goggles is Footwear Chemical resistant and as specified by the workplace Footwear Chemical resistant andlenses as specified by thebeworkplace with methanol. Protection taking place. not worn working Other Eyewash and Contact showers shouldshould be located near workwhen areas. Other Eyewash and showers should be located near work areas. Footwear Chemical resistant and as specified by the workplace with methanol. ! Eyewash showers be located work areas. ! Other Footwear Chemical and resistant andshould as specified by thenear workplace ! Other Eyewash and showers should be located near work areas. !
4
irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause irritation of the mucous membranes. a. Inhalation, rabbit: LC50 = 81000 mg/m3/14H; b. Inhalation, rat: LC50 = 64000 ppm/4H; 3- Methanol is a mild to moderate eye irritant. High vapour concentration or liquid eye contact causes irritation, tearing and burning. Draize test on Rabbit eye a. 40 mg Moderate b. 100 mg/24H Moderate 4- Methanol is moderately irritating to the skin. Methanol can be absorbed through the skin and harmful effects have been reported by this route of entry. Effects are similar to those described in Inhalation. a. Draize test, rabbit, skin: 20 mg/24H Moderate b. Skin, rabbit : LD50 = 15800 mg/kg; 1- Swallowing even small amounts of methanol could potentially or death. of Effects of sub could lethal 1- Swallowingcause evenblindness small amounts methanol doses may be blindness nausea, or headache, abdominal pain, potentially cause death. Effects of sub lethal vomiting and be visual disturbances ranging from blurred doses may nausea, headache, abdominal pain, vision to light vomiting and sensitivity. visual disturbances ranging from blurred a. Oral, mouse: LD50 = 7300 mg/kg; vision to light sensitivity. b. mg/kg; a. Oral, Oral, rabbit: mouse: LD50 LD50==14200 7300 mg/kg; c. LD50 = 5600 mg/kg; b. Oral, Oral, rat: rabbit: LD50 = 14200 mg/kg; d. 143 mg/kg; Human LDLo Oral: c. Human Oral, rat:LDLo LD50Oral: = 5600 mg/kg; 428 mg/kg; Human TCLo Inhalation; 300 Oral: ppm d. Human LDLo Oral: 143 mg/kg; Human LDLo caused 428 mg/kg; Human TCLo Inhalation; 300 ppm e. Monkey caused LDLo Skin: 393 mg/kg. Methanol is toxic most experimental e. significantly Monkey LDLoless Skin: 393to mg/kg. Methanol is animals thanless humans, animal significantly toxic because to most most experimental species metabolize methanol differently. animals than humans, because most animal f. Non-primate species do not ordinarily show species metabolize methanol differently. metabolic or the visual f. symptoms Non-primateof species do acidosis not ordinarily show effects which been observed and symptoms of have metabolic acidosis inorprimates the visual humans. effects which have been observed in primates and
Section 9. Physical and Chemical Properties Physical state and appearance: Odour: Molecular Weight: pH (1% soln/water): Boiling Point: Melting Point: Flash Point: Auto Ignition Temperature: Critical Temperature: Specific Gravity/ Density: Vapour Pressure: Vapour Density: Dispersion Properties: Solubility in Water: Solvent Solubility: Viscosity: Evaporation Rate: !
Clear liquid, clear, colourless - APHA: 10 max Alcohol-like - weak odour 32.04 g/mol Not available. 64.7 deg C @ 760 mmHg -98 oC 11.0 oC 464 oC
Eye Contact:
Skin Contact:
239.4 oC. 7910 g/cm3 @ 20°C 12.8 KPa @ 20 oC
Ingestion: Ingestion:
1.105 @ 15 oC (Air=1) See solubility in water. Completely miscible. Soluble in all proportions in ethanol, benzene, other alcohols, chloroform, diethyl ether, other ethers, esters, ketones and most organic solvents. 0.55 cP 20 oC 5.2 (Ether=1)
Section 10. Stability and Reactivity Data Stability:
Stable under normal temperatures and pressures.
Incompatibility with various substances:
Oxidizing agents, reducing agents, acids, alkali metals, potassium, sodium, metals as powders (e.g. hafnium, raney nickel), acid anhydrides, acid chlorides, powdered aluminium, powdered magnesium.
Instability Temperature:
Not available.
Conditions to avoid:
Avoid high temperatures, ignition sources, sparks, confined spaces.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, formaldehyde.
Polymerization:
Will not occur.
Possibility of Avoid contact with strong oxidizers, strong mineral or organic Hazardous acids and strong bases. Contact with these materials may cause Reactions: a violent or explosive reaction. ! Section 11.11. Toxicological Information Section Toxicological Information RTECS#: Primary Routes of Entry Acute Exposure: Inhalation
5
Chronic Exposure Chronic Irritancy Exposure
Irritancy Sensitisation: Carcinogenicity: Sensitisation: Teratogenicity: Carcinogenicity: Teratogenicity: Reproductive Toxicity: Reproductive Mutagenicity: Toxicity: Neurotoxicity: Mutagenicity:
humans.
Prolonged contact with skin may defat tissue causing dermatitis or aggravate existing skin problems. Prolonged contact with skin may defat tissue causing dermatitis None reported. or aggravate existing skin problems. Not listed by ACGIH, IARC, NTP as a carcinogen. None reported. There is byno human available. Methanol is Not listed ACGIH, IARC,information NTP as a carcinogen. considered to behuman a potential developmental hazard based on There is no information available. Methanol is animal data.to In experiments, methanol hasbased caused considered be animal a potential developmental hazard on fetotoxicity or teratogenic withoutmethanol maternal toxicity. animal data. In animal effects experiments, has caused Information oravailable does not without suggestmaternal that methanol fetotoxicity teratogenic effects toxicity. is a reproductive toxin. Information available does not suggest that methanol is a See actual entry in RTECS for complete information. reproductive toxin. ACGIH cites neuropathy, and CNSinformation. under TLV basis. See actual entry in RTECSvision for complete
Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis. Section 12. Ecological Information
Section 12. Ecological Information Ecotoxicity:
Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified); Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 degrees C; LC50 = 8000 mg/L; 48 Hr.; Unspecified Goldfish: 250 ppm; 11 Hr; resulted in death Fish: 8000 mg/L; 48 Hr; LC50 (unspecified) Bacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L; 30 minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization 1- 19,500 mg/ltr/18 hr; static 22 DegC, 2- 23,500 mg/ltr/24 hr 3- 22,200 mg/ltr/48 hr
Log Kow: Half Life(hr) air: Half Life(hr) H2O:
-0.82 to -0.66 427 5.3 - 64
PC1400000 1- Skin Contact; Skin Absorption; Eye Contact; Ingestion; Inhalation; 2- Inhalation of high airborne concentrations can also irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause
minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization 1. 19,500 mg/ltr/18 hr; static 22 DegC, 2. 23,500 mg/ltr/24 hr 3. 22,200 mg/ltr/48 hr Log Kow: -0.82 to -0.66 Half Life(hr) air: 427 Half Life(hr) H2O: 5.3 - 64 Surface water: Henry’s Law 4.55 X 10-6 Constant (atm m3/mol) BOD5 0.76-1.12 COD 1.0-1.5. 99% ThOD 1.05 Biological 0.2-1.0 Concentration Factor (BCF) TLm (48 hr) 8000 mg/ltr (trout) Toxicity NOEL 10 g/L/48 hr (Daphnia) Anthropoda HSNO 9.3 Harmful to Terrestrial vertebrates Classification: Methanol in Fresh Water or salt water may have serious effects on aquatic life. A study on methanol’s toxic effects on sewage sludge bacteria reported little effect on digestion at 0.1% while 0.5% methanol retarded digestion. Methanol will be broken down into carbon dioxide and water. Environmental Fate:
Atmospheric Fate:
conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments. Methanol is expected to exist solely as a vapour in the ambient atmosphere. Vapour–phase methanol is degraded in the atmosphere, by reaction with photo chemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 17 days, calculated from its rate constant of 9.4 X 10-13cucm/molecule-sec at 25 oC.
!
Section 13. Disposal Considerations Waste Disposal:
•
Waste Disposal:
••
Resource Conservation Resource and Recovery Conservation Act (RCRA) Uand Recovery Series: Act (RCRA) U! Series: !
Disposal shall comply to the federal, provincial and local government’s statutory requirement. Empty containers may to contain hazardous residue. Disposal shall comply the federal, provincial andReturn local to supplier for reuse if possible. Never weld, cut or grind empty government’s statutory requirement. containers. • Empty containers may contain hazardous residue. Return to • While disposing containers make sure thatcut they well supplier for reuse if possible. Never weld, or are grind empty rinsed with water and then disposed of at an authorised containers. landfill. After cleaning all themake labels to be removed. • While disposing containers sure that they are well Waste number U154 (Ignitable waste). of at an authorised rinsed with water and then disposed landfill. After cleaning all the labels to be removed. Waste number U154 (Ignitable waste).
Section 14. Transport Information Dangerous to aquatic life in high concentrations. Aquatic toxicity rating: TLm 96>1000 ppm. May be dangerous if it enters water intakes. Methyl alcohol is expected to biodegrade in soil and water very rapidly. This product will show high soil mobility and will be degraded from the ambient atmosphere by the reaction with photochemically produced hyroxyl radicals with an estimated half-life of 17.8 days. Bioconcentration factor for fish (golden ide) < 10. Based on a log Kow of -0.77, the BCF value for methanol can be estimated to be 0.2. Biodegrades easily in water and soil.
Biodegradability: Bioaccumulation: Terrestrial fate: Based on a classification scheme, an estimated Koc value of 1 determined from a structure estimation method indicates that methanol is expected to have very high mobility in soil. Volatilization of methanol from moist soil surfaces is expected to be an important fate process given a Henry’s Law constant of 4.55 X 10-6 atm m3/mol. The potential of volatilization of methanol from dry soil surfaces may exist based upon a vapour pressure of 127 mmHg. Biodegratation is expected to be an important fate process for methanol. Aquatic Fate: Methanol is not expected to adsorb to suspended solids and sediment. Volatilization from water surfaces is expected based upon a Henry’s Law constant 4.55 X 10-6 atm m3/mol. Volatilization halflives for a model river and model lake are three and 35 day, respectively. According to a classification scheme, a BCF of less than 10 measured in fish, suggests bioconcentration in aquatic organisms is low. Hydrolysis and photolysis in sunlit surface waters is not expected to be an important environmental fate process for methanol since this compound lacks functional groups that hydrolyze or absorb light under environmentally relevant conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments.
Shipping Shipping Name: Name: Hazard Hazard Class: Class: UN UN Number: Number: Packing Packing Group: Group: Additional Additional Information: Information:
US US DOT DOT CANADA CANADA TDG TDG Methanol Methanol Methanol Methanol 33 33 UN1230 UN1230 UN1230 UN1230 IIII IIII Reportable Reportable Quantity Quantity (RQ) (RQ) 5000 5000 Flash Flash Point Point 12" 12" lbs lbs (2270 (2270 kg) kg) ERG ERG Guide Guide Number: Number: 131 131 Limited Limited Quantity Quantity !! 11 litre litre
Shipping Shipping Name: Name: Hazard Hazard Cl#ss: Cl#ss: UN UN Number: Number: Packing Packing G#oup: G#oup: Additional Additional Information: Information:
IATA IATA Methanol Methanol 33 UN1230 UN1230 IIII 1. 1. Packaging Packaging Instruction Instruction (passenger (passenger aircraft) aircraft) 305 305 2. 2. 11 litre litre maximum maximum package package
!!
IMO IMO Methanol Methanol 33 UN1230 UN1230 IIII 1. 1. Flash Flash point point == 11 11 °C °C 2. 2. EmS EmS No No F-E, F-E, S-D S-D 3. 3. Stowage Stowage Category Category “,B” “,B” 4. 4. Clear Clear of of living living quarters quarters
GPIC is committed to Protect & sustain product stewardship 6
irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause irritation of the mucous membranes. a. Inhalation, rabbit: LC50 = 81000 mg/m3/14H; b. Inhalation, rat: LC50 = 64000 ppm/4H; 3- Methanol is a mild to moderate eye irritant. High vapour concentration or liquid eye contact causes irritation, tearing and burning. Draize test on Rabbit eye a. 40 mg Moderate b. 100 mg/24H Moderate 4- Methanol is moderately irritating to the skin. Methanol can be absorbed through the skin and harmful effects have been reported by this route of entry. Effects are similar to those described in Inhalation. a. Draize test, rabbit, skin: 20 mg/24H Moderate b. Skin, rabbit : LD50 = 15800 mg/kg; 1- Swallowing even small amounts of methanol could potentially or death. of Effects of sub could lethal 1- Swallowingcause evenblindness small amounts methanol doses may be blindness nausea, or headache, abdominal pain, potentially cause death. Effects of sub lethal vomiting and be visual disturbances ranging from blurred doses may nausea, headache, abdominal pain, vision to light vomiting and sensitivity. visual disturbances ranging from blurred a. Oral, mouse: LD50 = 7300 mg/kg; vision to light sensitivity. b. mg/kg; a. Oral, Oral, rabbit: mouse: LD50 LD50==14200 7300 mg/kg; c. LD50 = 5600 mg/kg; b. Oral, Oral, rat: rabbit: LD50 = 14200 mg/kg; d. 143 mg/kg; Human LDLo Oral: c. Human Oral, rat:LDLo LD50Oral: = 5600 mg/kg; 428 mg/kg; Human TCLo Inhalation; 300 Oral: ppm d. Human LDLo Oral: 143 mg/kg; Human LDLo caused 428 mg/kg; Human TCLo Inhalation; 300 ppm e. Monkey caused LDLo Skin: 393 mg/kg. Methanol is toxic most experimental e. significantly Monkey LDLoless Skin: 393to mg/kg. Methanol is animals thanless humans, animal significantly toxic because to most most experimental species metabolize methanol differently. animals than humans, because most animal f. Non-primate species do not ordinarily show species metabolize methanol differently. metabolic or the visual f. symptoms Non-primateof species do acidosis not ordinarily show effects which been observed and symptoms of have metabolic acidosis inorprimates the visual humans. effects which have been observed in primates and
Section 9. Physical and Chemical Properties Physical state and appearance: Odour: Molecular Weight: pH (1% soln/water): Boiling Point: Melting Point: Flash Point: Auto Ignition Temperature: Critical Temperature: Specific Gravity/ Density: Vapour Pressure: Vapour Density: Dispersion Properties: Solubility in Water: Solvent Solubility: Viscosity: Evaporation Rate: !
Clear liquid, clear, colourless - APHA: 10 max Alcohol-like - weak odour 32.04 g/mol Not available. 64.7 deg C @ 760 mmHg -98 oC 11.0 oC 464 oC
Eye Contact:
Skin Contact:
239.4 oC. 7910 g/cm3 @ 20°C 12.8 KPa @ 20 oC
Ingestion: Ingestion:
1.105 @ 15 oC (Air=1) See solubility in water. Completely miscible. Soluble in all proportions in ethanol, benzene, other alcohols, chloroform, diethyl ether, other ethers, esters, ketones and most organic solvents. 0.55 cP 20 oC 5.2 (Ether=1)
Section 10. Stability and Reactivity Data Stability:
Stable under normal temperatures and pressures.
Incompatibility with various substances:
Oxidizing agents, reducing agents, acids, alkali metals, potassium, sodium, metals as powders (e.g. hafnium, raney nickel), acid anhydrides, acid chlorides, powdered aluminium, powdered magnesium.
Instability Temperature:
Not available.
Conditions to avoid:
Avoid high temperatures, ignition sources, sparks, confined spaces.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, formaldehyde.
Polymerization:
Will not occur.
Possibility of Avoid contact with strong oxidizers, strong mineral or organic Hazardous acids and strong bases. Contact with these materials may cause Reactions: a violent or explosive reaction. ! Section 11.11. Toxicological Information Section Toxicological Information RTECS#: Primary Routes of Entry Acute Exposure: Inhalation
5
Chronic Exposure Chronic Irritancy Exposure
Irritancy Sensitisation: Carcinogenicity: Sensitisation: Teratogenicity: Carcinogenicity: Teratogenicity: Reproductive Toxicity: Reproductive Mutagenicity: Toxicity: Neurotoxicity: Mutagenicity:
humans.
Prolonged contact with skin may defat tissue causing dermatitis or aggravate existing skin problems. Prolonged contact with skin may defat tissue causing dermatitis None reported. or aggravate existing skin problems. Not listed by ACGIH, IARC, NTP as a carcinogen. None reported. There is byno human available. Methanol is Not listed ACGIH, IARC,information NTP as a carcinogen. considered to behuman a potential developmental hazard based on There is no information available. Methanol is animal data.to In experiments, methanol hasbased caused considered be animal a potential developmental hazard on fetotoxicity or teratogenic withoutmethanol maternal toxicity. animal data. In animal effects experiments, has caused Information oravailable does not without suggestmaternal that methanol fetotoxicity teratogenic effects toxicity. is a reproductive toxin. Information available does not suggest that methanol is a See actual entry in RTECS for complete information. reproductive toxin. ACGIH cites neuropathy, and CNSinformation. under TLV basis. See actual entry in RTECSvision for complete
Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis. Section 12. Ecological Information
Section 12. Ecological Information Ecotoxicity:
Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified); Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 degrees C; LC50 = 8000 mg/L; 48 Hr.; Unspecified Goldfish: 250 ppm; 11 Hr; resulted in death Fish: 8000 mg/L; 48 Hr; LC50 (unspecified) Bacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L; 30 minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization 1- 19,500 mg/ltr/18 hr; static 22 DegC, 2- 23,500 mg/ltr/24 hr 3- 22,200 mg/ltr/48 hr
Log Kow: Half Life(hr) air: Half Life(hr) H2O:
-0.82 to -0.66 427 5.3 - 64
PC1400000 1- Skin Contact; Skin Absorption; Eye Contact; Ingestion; Inhalation; 2- Inhalation of high airborne concentrations can also irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause
minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization 1. 19,500 mg/ltr/18 hr; static 22 DegC, 2. 23,500 mg/ltr/24 hr 3. 22,200 mg/ltr/48 hr Log Kow: -0.82 to -0.66 Half Life(hr) air: 427 Half Life(hr) H2O: 5.3 - 64 Surface water: Henry’s Law 4.55 X 10-6 Constant (atm m3/mol) BOD5 0.76-1.12 COD 1.0-1.5. 99% ThOD 1.05 Biological 0.2-1.0 Concentration Factor (BCF) TLm (48 hr) 8000 mg/ltr (trout) Toxicity NOEL 10 g/L/48 hr (Daphnia) Anthropoda HSNO 9.3 Harmful to Terrestrial vertebrates Classification: Methanol in Fresh Water or salt water may have serious effects on aquatic life. A study on methanol’s toxic effects on sewage sludge bacteria reported little effect on digestion at 0.1% while 0.5% methanol retarded digestion. Methanol will be broken down into carbon dioxide and water. Environmental Fate:
Atmospheric Fate:
conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments. Methanol is expected to exist solely as a vapour in the ambient atmosphere. Vapour–phase methanol is degraded in the atmosphere, by reaction with photo chemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 17 days, calculated from its rate constant of 9.4 X 10-13cucm/molecule-sec at 25 oC.
!
Section 13. Disposal Considerations Waste Disposal:
•
Waste Disposal:
••
Resource Conservation Resource and Recovery Conservation Act (RCRA) Uand Recovery Series: Act (RCRA) U! Series: !
Disposal shall comply to the federal, provincial and local government’s statutory requirement. Empty containers may to contain hazardous residue. Disposal shall comply the federal, provincial andReturn local to supplier for reuse if possible. Never weld, cut or grind empty government’s statutory requirement. containers. • Empty containers may contain hazardous residue. Return to • While disposing containers make sure thatcut they well supplier for reuse if possible. Never weld, or are grind empty rinsed with water and then disposed of at an authorised containers. landfill. After cleaning all themake labels to be removed. • While disposing containers sure that they are well Waste number U154 (Ignitable waste). of at an authorised rinsed with water and then disposed landfill. After cleaning all the labels to be removed. Waste number U154 (Ignitable waste).
Section 14. Transport Information Dangerous to aquatic life in high concentrations. Aquatic toxicity rating: TLm 96>1000 ppm. May be dangerous if it enters water intakes. Methyl alcohol is expected to biodegrade in soil and water very rapidly. This product will show high soil mobility and will be degraded from the ambient atmosphere by the reaction with photochemically produced hyroxyl radicals with an estimated half-life of 17.8 days. Bioconcentration factor for fish (golden ide) < 10. Based on a log Kow of -0.77, the BCF value for methanol can be estimated to be 0.2. Biodegrades easily in water and soil.
Biodegradability: Bioaccumulation: Terrestrial fate: Based on a classification scheme, an estimated Koc value of 1 determined from a structure estimation method indicates that methanol is expected to have very high mobility in soil. Volatilization of methanol from moist soil surfaces is expected to be an important fate process given a Henry’s Law constant of 4.55 X 10-6 atm m3/mol. The potential of volatilization of methanol from dry soil surfaces may exist based upon a vapour pressure of 127 mmHg. Biodegratation is expected to be an important fate process for methanol. Aquatic Fate: Methanol is not expected to adsorb to suspended solids and sediment. Volatilization from water surfaces is expected based upon a Henry’s Law constant 4.55 X 10-6 atm m3/mol. Volatilization halflives for a model river and model lake are three and 35 day, respectively. According to a classification scheme, a BCF of less than 10 measured in fish, suggests bioconcentration in aquatic organisms is low. Hydrolysis and photolysis in sunlit surface waters is not expected to be an important environmental fate process for methanol since this compound lacks functional groups that hydrolyze or absorb light under environmentally relevant conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments.
Shipping Shipping Name: Name: Hazard Hazard Class: Class: UN UN Number: Number: Packing Packing Group: Group: Additional Additional Information: Information:
US US DOT DOT CANADA CANADA TDG TDG Methanol Methanol Methanol Methanol 33 33 UN1230 UN1230 UN1230 UN1230 IIII IIII Reportable Reportable Quantity Quantity (RQ) (RQ) 5000 5000 Flash Flash Point Point 12" 12" lbs lbs (2270 (2270 kg) kg) ERG ERG Guide Guide Number: Number: 131 131 Limited Limited Quantity Quantity !! 11 litre litre
Shipping Shipping Name: Name: Hazard Hazard Cl#ss: Cl#ss: UN UN Number: Number: Packing Packing G#oup: G#oup: Additional Additional Information: Information:
IATA IATA Methanol Methanol 33 UN1230 UN1230 IIII 1. 1. Packaging Packaging Instruction Instruction (passenger (passenger aircraft) aircraft) 305 305 2. 2. 11 litre litre maximum maximum package package
!!
IMO IMO Methanol Methanol 33 UN1230 UN1230 IIII 1. 1. Flash Flash point point == 11 11 °C °C 2. 2. EmS EmS No No F-E, F-E, S-D S-D 3. 3. Stowage Stowage Category Category “,B” “,B” 4. 4. Clear Clear of of living living quarters quarters
GPIC is committed to Protect & sustain product stewardship 6
Section 15. Other Regulatory Information Toxic Substances Control Act (TSCA): Health & Safety Reporting List: Chemical Test Rules Section 12b:
Listed on the TSCA inventory. Not listed in the Health & Safety Reporting List. None of the chemicals in this product are under a Chemical Test Rule. None of the chemicals are listed under TSCA Section 12b. Reportable Quantity (RQ) 5000 lb (2270 kg)
CERCLA Hazardous Substances and corresponding RQs Superfund Amendment and Reauthorization Act (SARA) SARA Codes Section 302 None of the chemicals in this product have a Extremely Hazardous Threshold Planning Quantity (TPQ) Substances SARA Codes Immediate, fire. Section 313 This material contains methanol which is subject to the reporting requirements of Section 313 of SARA Title III and 40 CFR Part 373. Clean Air Act(CAA): Listed as a hazardous air pollutant (HAP). This material does not contain any Class 1 Ozone depletors. This material does not contain any Class 2 Ozone depletors. Clean Water Act (CWA): • None of the chemicals in this product are listed as Hazardous Substances under the CWA. • None of the chemicals in this product are listed as Priority Pollutants under the CWA. • None of the chemicals in this product are listed as Toxic Pollutants under the CWA. OSHA: None of the chemicals in this product are considered highly hazardous by OSHA.
Section 16. Other Information Disclaimer: Disclaimer: This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 and contains information believed to be accurate and complete at the date of and contains information believed to offered be accurate and complete at the date of preparation. The statements contained herein are for informational purposes preparation. The statements only and are based upon technical data.contained herein are offered for informational purposes only and aretobased upon technical data. GPIC believes them be accurate but does not purport to be all-inclusive. The GPIC believes them to to be be accurate accurate and but does not purport to information be all-inclusive. The information above is believed represents the best information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any currently available to us. with However, wetomake warranty and of merchantability or any other warranty, express or implied, respect such no information, we assume warranty, express no liabilityother resulting from its use. or implied, with respect to such information, and we assume no liability from its use. Users should make resulting their own investigations to determine the suitability of the Users should makepurposes. their own investigations to determine the suitability of the information for their particular information for their particular purposes. In no event shall GPIC be liable for any claims, losses, or damages of any third party In no event shall GPIC be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary for lost profits oreven any special, indirect, damages, or whatsoever arising, if GPIC has been incidental, advised ofconsequential the possibilityorofexemplary damages, whatsoever arising, even if GPIC has been advised of the possibility of such damages. such damages. Revised: All sections have been revised on 16th August, th 2012. Revised: All sections have been revised on 16 August, 2012. 1- GPIC’s Products Handling & Export Facility: 1- GPIC’s Products Handling & Export Facility:
4- GPIC’s Products Handling & Export Facility GPIC’s storage facilities comprise two storage tanks which serve to contain / hold the methanol that will be supplied from the intermediate storage. Each tank has a storage capacity of 20,000 tonnes. Methanol is transferred from the tanks to the ship by means of loading pumps. Generally, two pumps are required for ship loading while the third pump serves as a standby at a maximum loading rate of 1200 MT/HR through a dedicated export line of 16” diameter and approximately 4 km long.
load methanol into ships. Two methanol loading arms are provided, one at Berth No.1 and one at Berth No.2, which are operated hydraulically to move the arm to the appropriate position for connection to the ship manifold. Provision is also available for loading methanol into road tankers for local sale upon special request.
GPIC utilises the Sitra wharf owned by BAPCO to
European/International Regulations European Labelling in Accordance Hazard Symbols: • Risk Phrases: • •
Safety Phrases: Safety Phrases:
WGK (Water Danger/Protection) Canada - DSL/NDSL Canada – WHMIS:
Canadian Ingredient Disclosure List: !
5 7
with EC Directives TF R 11 Highly flammable. R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed. • R 39/23/24/25 Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. • S 16 Keep away from sources of ignition - No smoking. •• S Keep away from sources of clothing ignition -and No S 16 36/37 Wear suitable protective smoking. gloves. •• S 36/37 Wear suitable protective clothing and S 45 In case of accident or if you feel unwell, gloves. • S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). • S 7 Keep container tightly closed. Low Danger to Water – (1) Listed on Canada's DSL List. This product has a WHMIS classification of B2, D1B, D2B. This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations and the MSDS contains all of the information required by the regulations. Listed on the Canadian Ingredient Disclosure List.
8
Section 15. Other Regulatory Information Toxic Substances Control Act (TSCA): Health & Safety Reporting List: Chemical Test Rules Section 12b:
Listed on the TSCA inventory. Not listed in the Health & Safety Reporting List. None of the chemicals in this product are under a Chemical Test Rule. None of the chemicals are listed under TSCA Section 12b. Reportable Quantity (RQ) 5000 lb (2270 kg)
CERCLA Hazardous Substances and corresponding RQs Superfund Amendment and Reauthorization Act (SARA) SARA Codes Section 302 None of the chemicals in this product have a Extremely Hazardous Threshold Planning Quantity (TPQ) Substances SARA Codes Immediate, fire. Section 313 This material contains methanol which is subject to the reporting requirements of Section 313 of SARA Title III and 40 CFR Part 373. Clean Air Act(CAA): Listed as a hazardous air pollutant (HAP). This material does not contain any Class 1 Ozone depletors. This material does not contain any Class 2 Ozone depletors. Clean Water Act (CWA): • None of the chemicals in this product are listed as Hazardous Substances under the CWA. • None of the chemicals in this product are listed as Priority Pollutants under the CWA. • None of the chemicals in this product are listed as Toxic Pollutants under the CWA. OSHA: None of the chemicals in this product are considered highly hazardous by OSHA.
Section 16. Other Information Disclaimer: Disclaimer: This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 and contains information believed to be accurate and complete at the date of and contains information believed to offered be accurate and complete at the date of preparation. The statements contained herein are for informational purposes preparation. The statements only and are based upon technical data.contained herein are offered for informational purposes only and aretobased upon technical data. GPIC believes them be accurate but does not purport to be all-inclusive. The GPIC believes them to to be be accurate accurate and but does not purport to information be all-inclusive. The information above is believed represents the best information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any currently available to us. with However, wetomake warranty and of merchantability or any other warranty, express or implied, respect such no information, we assume warranty, express no liabilityother resulting from its use. or implied, with respect to such information, and we assume no liability from its use. Users should make resulting their own investigations to determine the suitability of the Users should makepurposes. their own investigations to determine the suitability of the information for their particular information for their particular purposes. In no event shall GPIC be liable for any claims, losses, or damages of any third party In no event shall GPIC be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary for lost profits oreven any special, indirect, damages, or whatsoever arising, if GPIC has been incidental, advised ofconsequential the possibilityorofexemplary damages, whatsoever arising, even if GPIC has been advised of the possibility of such damages. such damages. Revised: All sections have been revised on 16th August, th 2012. Revised: All sections have been revised on 16 August, 2012. 1- GPIC’s Products Handling & Export Facility: 1- GPIC’s Products Handling & Export Facility:
4- GPIC’s Products Handling & Export Facility GPIC’s storage facilities comprise two storage tanks which serve to contain / hold the methanol that will be supplied from the intermediate storage. Each tank has a storage capacity of 20,000 tonnes. Methanol is transferred from the tanks to the ship by means of loading pumps. Generally, two pumps are required for ship loading while the third pump serves as a standby at a maximum loading rate of 1200 MT/HR through a dedicated export line of 16” diameter and approximately 4 km long.
load methanol into ships. Two methanol loading arms are provided, one at Berth No.1 and one at Berth No.2, which are operated hydraulically to move the arm to the appropriate position for connection to the ship manifold. Provision is also available for loading methanol into road tankers for local sale upon special request.
GPIC utilises the Sitra wharf owned by BAPCO to
European/International Regulations European Labelling in Accordance Hazard Symbols: • Risk Phrases: • •
Safety Phrases: Safety Phrases:
WGK (Water Danger/Protection) Canada - DSL/NDSL Canada – WHMIS:
Canadian Ingredient Disclosure List: !
5 7
with EC Directives TF R 11 Highly flammable. R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed. • R 39/23/24/25 Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. • S 16 Keep away from sources of ignition - No smoking. •• S Keep away from sources of clothing ignition -and No S 16 36/37 Wear suitable protective smoking. gloves. •• S 36/37 Wear suitable protective clothing and S 45 In case of accident or if you feel unwell, gloves. • S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). • S 7 Keep container tightly closed. Low Danger to Water – (1) Listed on Canada's DSL List. This product has a WHMIS classification of B2, D1B, D2B. This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations and the MSDS contains all of the information required by the regulations. Listed on the Canadian Ingredient Disclosure List.
8
5-Port Rules & Requirements
6- Safety & Emergency Response
5.1 Location:
Ships must ensure maximum safety precautions are followed when loading at Sitra wharf and all crew members or visitors must wear appropriate personal protective equipment (PPE) at all times when the ship is alongside.
GPIC’s loading facilities are situated at Sitra wharf, which is owned by Bahrain Petroleum Company (BAPCO). The wharf also houses Bahrain Gas Company’s (BANAGAS) loading facility which includes 7 berths, two of which are each equipped with both an ammonia and a methanol loading arm (Berth No.1 and Berth No.2). The two loading arms at each berth allows GPIC to load either methanol or ammonia from any vacant berth of the two, based on their availability. Rules and regulations which are applicable to other ports within the Kingdom of Bahrain, are also applied to this port. As such, the port is subject to Customs and complies with the International Ship and Port Facility Security code (ISPS). All personnel using this port are subject to Immigration and Customs Controls pertaining to such a facility.
• A ship’s crew members must be subjected to a Sitra port Security search prior to exit from or entry to the port. • Shore personnel and contractors are strictly prohibited from receiving or delivering goods/items to ship’s crew members.
6.2 Useful facts about Methanol
To ensure maximum safety at Sitra Wharf, several precautions have been set.
• Methanol burns with a clear flame and without smoke, so it is difficult to see in daylight. Methanol will still burn at four parts of water to one part of methanol. The fire may be detected by the heat generated, a heat haze, or burning of materials in the affected area.
• Unauthorised personnel not involved in the loading operation are restricted from boarding the ships.
• A total of 15 remote operated high firefighting monitors have been distributed at the wharf.
5.3 Ship-Shore Pre-Loading Meeting In order to achieve a smooth, efficient and safe operation and so that all security requirements are fully understood, acknowledged and implemented by the ship’s personnel; a meeting is conducted between shore and ship representatives prior to commencement of loading operations.
• Two foam tanks with pumps and operating panels are situated at each side of the jetty.
To facilitate this, shore representatives and the ship’s Master/Chief Officer will jointly complete a number of forms/letters as listed below: • Smoking location onboard vessel.
• Five fire water pumps are located at the trestle entrance. (3 main pumps and 2 jockey pumps). • GPIC provides additional mobile fire water monitors at each side of the jetty, equipped with foam tanks for quick intervention during any emergency. • Break glass fire alarms have been provided at each side of the jetty. • 12 escape masks have been placed at each side of the jetty.
5.2 Security Requirements:
• Loading arm safe working area.
• Fire blankets and eye wash stations/showers are located at both sides of the jetty.
Ships calling at Sitra Marine Port to load methanol must declare their security level according to the ISPS code.
• Safety requirements for vessel loading at Sitra.
• 7 breathing apparatuses (7 Ltrs each) are located at
• Ships’ crews are not allowed to enter or exit the Sitra wharf without authorisation from the Immigration Office. • Visitors to ships must obtain clearance from the Immigration Office through the ship’s agent before allowed access. • Goods to and from ships must be cleared by the Customs Officer and inspected by Sitra port Security. • A ship’s crew members are not allowed to proceed from ship to shore without being accompanied by the ship’s agent representatives. 9
6.1 Safety:
• Ship/Shore log sheet. • Ship/Shore Safety check list. • Receipt of Material Safety Data Sheet. • ISPS form (counter signed by terminal security officer). All the above aspects will be discussed and mutually agreed between the ship and shore representatives, any controversial point must be authorised and countersigned by both parties. Also, a radio hand set is handed over to the ship for communication during loading operations.
the South side office.
• 4 spare oxygen cylinders have been provided at the South office. • One gas suit, two fire suits and two chemical suits have been provided at the South office as well.
• When transferring or storing methanol, dedicated systems are preferable. Non-dedicated systems should be cleaned, flushed and sampled before being used, in order to ensure product integrity. Equipment should be clearly labelled to indicate that it is for methanol service only. When not in use, the equipment must be protected from contamination. • Whenever possible, contain land spills by forming mechanical or chemical barriers. Remove spilled product with explosion proof pumps or vacuum equipment. Treat the surface with sorbent materials, such as vermiculite or activated carbon, to remove the remaining methanol. Remove the sorbents after use. Soil contaminated with methanol should be removed and remediated. • Spills into large natural bodies of water, such as rivers and oceans, cannot be recovered. Whenever possible, contain spills to small surface waters using natural or mechanical barriers. Then remove the contained material with explosion proof pumps or vacuum equipment. 6.3 Emergency Response:
• CO2 and dry powder extinguishers have been made available at the South office.
In case of emergency, the following actions are to be taken:
• When a Methanol ship is planned for berthing, all maintenance activities will be suspended, and entry to Sitra wharf will be under control.
• Call the emergency response telephone number as indicated. • If no access to a telephone, use a VHF radio to announce
10
5-Port Rules & Requirements
6- Safety & Emergency Response
5.1 Location:
Ships must ensure maximum safety precautions are followed when loading at Sitra wharf and all crew members or visitors must wear appropriate personal protective equipment (PPE) at all times when the ship is alongside.
GPIC’s loading facilities are situated at Sitra wharf, which is owned by Bahrain Petroleum Company (BAPCO). The wharf also houses Bahrain Gas Company’s (BANAGAS) loading facility which includes 7 berths, two of which are each equipped with both an ammonia and a methanol loading arm (Berth No.1 and Berth No.2). The two loading arms at each berth allows GPIC to load either methanol or ammonia from any vacant berth of the two, based on their availability. Rules and regulations which are applicable to other ports within the Kingdom of Bahrain, are also applied to this port. As such, the port is subject to Customs and complies with the International Ship and Port Facility Security code (ISPS). All personnel using this port are subject to Immigration and Customs Controls pertaining to such a facility.
• A ship’s crew members must be subjected to a Sitra port Security search prior to exit from or entry to the port. • Shore personnel and contractors are strictly prohibited from receiving or delivering goods/items to ship’s crew members.
6.2 Useful facts about Methanol
To ensure maximum safety at Sitra Wharf, several precautions have been set.
• Methanol burns with a clear flame and without smoke, so it is difficult to see in daylight. Methanol will still burn at four parts of water to one part of methanol. The fire may be detected by the heat generated, a heat haze, or burning of materials in the affected area.
• Unauthorised personnel not involved in the loading operation are restricted from boarding the ships.
• A total of 15 remote operated high firefighting monitors have been distributed at the wharf.
5.3 Ship-Shore Pre-Loading Meeting In order to achieve a smooth, efficient and safe operation and so that all security requirements are fully understood, acknowledged and implemented by the ship’s personnel; a meeting is conducted between shore and ship representatives prior to commencement of loading operations.
• Two foam tanks with pumps and operating panels are situated at each side of the jetty.
To facilitate this, shore representatives and the ship’s Master/Chief Officer will jointly complete a number of forms/letters as listed below: • Smoking location onboard vessel.
• Five fire water pumps are located at the trestle entrance. (3 main pumps and 2 jockey pumps). • GPIC provides additional mobile fire water monitors at each side of the jetty, equipped with foam tanks for quick intervention during any emergency. • Break glass fire alarms have been provided at each side of the jetty. • 12 escape masks have been placed at each side of the jetty.
5.2 Security Requirements:
• Loading arm safe working area.
• Fire blankets and eye wash stations/showers are located at both sides of the jetty.
Ships calling at Sitra Marine Port to load methanol must declare their security level according to the ISPS code.
• Safety requirements for vessel loading at Sitra.
• 7 breathing apparatuses (7 Ltrs each) are located at
• Ships’ crews are not allowed to enter or exit the Sitra wharf without authorisation from the Immigration Office. • Visitors to ships must obtain clearance from the Immigration Office through the ship’s agent before allowed access. • Goods to and from ships must be cleared by the Customs Officer and inspected by Sitra port Security. • A ship’s crew members are not allowed to proceed from ship to shore without being accompanied by the ship’s agent representatives. 9
6.1 Safety:
• Ship/Shore log sheet. • Ship/Shore Safety check list. • Receipt of Material Safety Data Sheet. • ISPS form (counter signed by terminal security officer). All the above aspects will be discussed and mutually agreed between the ship and shore representatives, any controversial point must be authorised and countersigned by both parties. Also, a radio hand set is handed over to the ship for communication during loading operations.
the South side office.
• 4 spare oxygen cylinders have been provided at the South office. • One gas suit, two fire suits and two chemical suits have been provided at the South office as well.
• When transferring or storing methanol, dedicated systems are preferable. Non-dedicated systems should be cleaned, flushed and sampled before being used, in order to ensure product integrity. Equipment should be clearly labelled to indicate that it is for methanol service only. When not in use, the equipment must be protected from contamination. • Whenever possible, contain land spills by forming mechanical or chemical barriers. Remove spilled product with explosion proof pumps or vacuum equipment. Treat the surface with sorbent materials, such as vermiculite or activated carbon, to remove the remaining methanol. Remove the sorbents after use. Soil contaminated with methanol should be removed and remediated. • Spills into large natural bodies of water, such as rivers and oceans, cannot be recovered. Whenever possible, contain spills to small surface waters using natural or mechanical barriers. Then remove the contained material with explosion proof pumps or vacuum equipment. 6.3 Emergency Response:
• CO2 and dry powder extinguishers have been made available at the South office.
In case of emergency, the following actions are to be taken:
• When a Methanol ship is planned for berthing, all maintenance activities will be suspended, and entry to Sitra wharf will be under control.
• Call the emergency response telephone number as indicated. • If no access to a telephone, use a VHF radio to announce
10
“EMERGENCY” three times.
• Suspend loading operation immediately. • As an immediate precautionary measure, isolate spill or leak area for at least 50 metres (150 feet) in all directions.
• Keep unauthorised personnel away. • Stay upwind. • Keep out of low areas. • Ventilate closed spaces before entering. • Personal Protective clothing: • Personal protective equipment for the responders should at a minimum include: - Wear positive pressure self-contained breathing apparatus (SCBA). - Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. - Structural firefighters’ protective clothing provides limited protection in fire situations ONLY, it is not effective in spills situations where direct contact with the substance is possible.
• Fire:
• Withdraw immediately in case of rising sound from venting safety devices or discolouration of tank. • Always stay away from tanks engulfed in fire. • For massive fires, use unmanned hose holders or monitor nozzles, if this is impossible, withdraw from area and let fire burn.
• Spill or Leak: • Fully encapsulating vapour protective clothing should be worn for spills and leaks with no fire. • Stop or reduce methanol release rate at the point of release if can be done safely. • If there are noxious vapours, evacuate, sound alarm and notify supervisor. • Eliminate all ignition sources to a safe standoff distance from the point of release and nearby methanol pooling. • All equipment used when handling the product must be grounded. • Do not touch or walk through spilled material.
• If Methanol ignition occurs in daylight hours, it is unlikely that the fire will be detected visually until it spreads to adjacent materials that emit a luminous flame or a visible plume of smoke.
• Stop leak if you can do it without risk.
• If a Methanol source is emitting large quantities of vapour, it is only a matter of time before ignition and flashback occurs.
• A vapour suppressing foam may be used to reduce vapours.
• Small fire: Use dry chemical, CO2, water spray or alcohol-resistant foam. • Large fire: - Water spray, fog or alcohol-resistant foam. - Move containers from fire area if you can do it without risk. - Dike fire-control water for later disposal. Do not scatter the material. - Use water spray or fog. Do not use straight streams.
• Fire involving tanks: • Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
11
• Cool containers with flooding quantities of water until well after fire is out.
• Prevent entry into waterways, sewers, basements or confined areas.
• Small spill: Absorb with earth, sand or other noncombustible material and transfer to containers for later disposal. And use clean non-sparking tools to collect absorbed material. • Large spill: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapour, but may not prevent ignition in closed spaces.
• First aid: • Move victim to fresh air. • Call emergency medical service. • Give artificial respiration if victim is not breathing.
ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. • Administer oxygen if breathing is difficult. • Remove and isolate contaminated clothing and shoes. • In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. • Wash skin with soap and water.
• In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.
• Keep victim warm and quiet. • Effects of exposure (inhalation, ingestion or skin
6.4 Environmental Factors:
• Methanol is biodegrades in low concentrations. • Methanol is soluble in water. • Do not dispose of methanol in the environment. • Impact is confined to the immediate area of the release. There is an adverse effect on water life - if the release is large enough.
• Contain the release, dispose of methanol safety. • Stay upwind of the release or fire. • Evacuate the area where the atmosphere is above acceptable limits,i.e.,200 ppm methanol in air, or if you can smell a faint odour of alcohol.
contact) to substance may be delayed.
• Ensure that the medical personnel are aware of the
materials involved and take precautions to protect themselves.
• Do not use mouth-to-mouth method if victim
12
“EMERGENCY” three times.
• Suspend loading operation immediately. • As an immediate precautionary measure, isolate spill or leak area for at least 50 metres (150 feet) in all directions.
• Keep unauthorised personnel away. • Stay upwind. • Keep out of low areas. • Ventilate closed spaces before entering. • Personal Protective clothing: • Personal protective equipment for the responders should at a minimum include: - Wear positive pressure self-contained breathing apparatus (SCBA). - Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. - Structural firefighters’ protective clothing provides limited protection in fire situations ONLY, it is not effective in spills situations where direct contact with the substance is possible.
• Fire:
• Withdraw immediately in case of rising sound from venting safety devices or discolouration of tank. • Always stay away from tanks engulfed in fire. • For massive fires, use unmanned hose holders or monitor nozzles, if this is impossible, withdraw from area and let fire burn.
• Spill or Leak: • Fully encapsulating vapour protective clothing should be worn for spills and leaks with no fire. • Stop or reduce methanol release rate at the point of release if can be done safely. • If there are noxious vapours, evacuate, sound alarm and notify supervisor. • Eliminate all ignition sources to a safe standoff distance from the point of release and nearby methanol pooling. • All equipment used when handling the product must be grounded. • Do not touch or walk through spilled material.
• If Methanol ignition occurs in daylight hours, it is unlikely that the fire will be detected visually until it spreads to adjacent materials that emit a luminous flame or a visible plume of smoke.
• Stop leak if you can do it without risk.
• If a Methanol source is emitting large quantities of vapour, it is only a matter of time before ignition and flashback occurs.
• A vapour suppressing foam may be used to reduce vapours.
• Small fire: Use dry chemical, CO2, water spray or alcohol-resistant foam. • Large fire: - Water spray, fog or alcohol-resistant foam. - Move containers from fire area if you can do it without risk. - Dike fire-control water for later disposal. Do not scatter the material. - Use water spray or fog. Do not use straight streams.
• Fire involving tanks: • Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
11
• Cool containers with flooding quantities of water until well after fire is out.
• Prevent entry into waterways, sewers, basements or confined areas.
• Small spill: Absorb with earth, sand or other noncombustible material and transfer to containers for later disposal. And use clean non-sparking tools to collect absorbed material. • Large spill: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapour, but may not prevent ignition in closed spaces.
• First aid: • Move victim to fresh air. • Call emergency medical service. • Give artificial respiration if victim is not breathing.
ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. • Administer oxygen if breathing is difficult. • Remove and isolate contaminated clothing and shoes. • In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. • Wash skin with soap and water.
• In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.
• Keep victim warm and quiet. • Effects of exposure (inhalation, ingestion or skin
6.4 Environmental Factors:
• Methanol is biodegrades in low concentrations. • Methanol is soluble in water. • Do not dispose of methanol in the environment. • Impact is confined to the immediate area of the release. There is an adverse effect on water life - if the release is large enough.
• Contain the release, dispose of methanol safety. • Stay upwind of the release or fire. • Evacuate the area where the atmosphere is above acceptable limits,i.e.,200 ppm methanol in air, or if you can smell a faint odour of alcohol.
contact) to substance may be delayed.
• Ensure that the medical personnel are aware of the
materials involved and take precautions to protect themselves.
• Do not use mouth-to-mouth method if victim
12
7-Glossary CAS No. : Each chemical has a discrete Chemical Abstracts
OSHA PEL : Permissible Exposure Limit. American equivalent
Service (CAS) registry number. This number will accurately
of TLV (Threshold Limit Value) and WES (Workplace Exposure
indicate the chemical being described.
Standards), as determined by the Occupational Safety
UN No. : United Nations Number.
This is the number
and Health Administration. (OSHA-USA)
allocated by the United Nations and is used internationally
TLV-TWA : Threshold Value Time Weighted Average: is
by emergency services to quickly identify a hazardous
defined as concentration of the substance in air that can
chemical in the event of an accident.
be breathed for five consecutive eight hour working days
Class 1: Explosives
(40 hour work week) by most people without adverse effect. ORL - RAT LD 50 : Values given are the concentrations or
Class 3: Flammable Liquids
a population of the rat model for inhalation and ingestion.
Class 5: Oxidizing agents and Organic Peroxides. Class 6: Poisonous (toxic) and infectious substances Class 7: Radioactive substances. Class 8: Corrosive Substances Class 9: Miscellaneous dangerous goods.
exceeded. It is not a separate independent exposure limit, rather it supplements the time - weighted average (TWA) limit where there are recognised acute effects from a substance where toxic effects are primarily of a chronic nature. STEL is defined as a 15-minute TWA exposure which should not be exceeded at any time during a working day even if the 8-hour TWA is within the TLV-TWA. Exposure above TLVTWA up to STEL should not be longer than 15 minutes and
Class 2: Gases: Compressed, Liquefied of Dissolved under pressure
Class 4: Flammable Solids, Substances liable to spontaneous combustion, Flammable substances if wetted
work efficiency, provided that the daily TLV-TWA is not
should not occur more than four times per day.
quantities of a chemical that will cause the death of 50% of
Hazchem Code :
The Hazchem Code is a code used
to identify the emergency response action in chemical related emergencies.
TLV-C : Threshold Limit Value-Ceiling - the concentration that should not be exceeded during any part of the working exposure.
Bio accumulation : Biological accumulation Eco Toxicity : Ecological Toxicity IDLH :
The Immediately Dangerous to Life and Health
value - This concentration represents a maximum level from which one could escape within 30 minutes without any escape - impairing symptoms or any irreversible health effects. The concentrations are reported in either parts per
UEL (Upper Explosive limit): The lowest concentration limits (normally measured in % volume to air) of a gas or vapour that will be able to support ignition and burn or explode.
million (PPM) or milligrams per cubic metre (mg/m3). TLV-STEL : Short Term Exposure Limit - The concentration to which it is believed that workers can be exposed
LEL (Lower Explosive Limit): The lowest concentration limits
continuously for a short period of time without suffering
(normally measured in % volume to air) of a gas or vapour
from 1) Irritation 2) Chronic or irreversible tissue damage or
that will be able to support ignition and burn or explode.
3) Narcosis of a sufficient degree to increase the likelihood of accidental injury, impair self-rescue or materially reduce
13
14
7-Glossary CAS No. : Each chemical has a discrete Chemical Abstracts
OSHA PEL : Permissible Exposure Limit. American equivalent
Service (CAS) registry number. This number will accurately
of TLV (Threshold Limit Value) and WES (Workplace Exposure
indicate the chemical being described.
Standards), as determined by the Occupational Safety
UN No. : United Nations Number.
This is the number
and Health Administration. (OSHA-USA)
allocated by the United Nations and is used internationally
TLV-TWA : Threshold Value Time Weighted Average: is
by emergency services to quickly identify a hazardous
defined as concentration of the substance in air that can
chemical in the event of an accident.
be breathed for five consecutive eight hour working days
Class 1: Explosives
(40 hour work week) by most people without adverse effect. ORL - RAT LD 50 : Values given are the concentrations or
Class 3: Flammable Liquids
a population of the rat model for inhalation and ingestion.
Class 5: Oxidizing agents and Organic Peroxides. Class 6: Poisonous (toxic) and infectious substances Class 7: Radioactive substances. Class 8: Corrosive Substances Class 9: Miscellaneous dangerous goods.
exceeded. It is not a separate independent exposure limit, rather it supplements the time - weighted average (TWA) limit where there are recognised acute effects from a substance where toxic effects are primarily of a chronic nature. STEL is defined as a 15-minute TWA exposure which should not be exceeded at any time during a working day even if the 8-hour TWA is within the TLV-TWA. Exposure above TLVTWA up to STEL should not be longer than 15 minutes and
Class 2: Gases: Compressed, Liquefied of Dissolved under pressure
Class 4: Flammable Solids, Substances liable to spontaneous combustion, Flammable substances if wetted
work efficiency, provided that the daily TLV-TWA is not
should not occur more than four times per day.
quantities of a chemical that will cause the death of 50% of
Hazchem Code :
The Hazchem Code is a code used
to identify the emergency response action in chemical related emergencies.
TLV-C : Threshold Limit Value-Ceiling - the concentration that should not be exceeded during any part of the working exposure.
Bio accumulation : Biological accumulation Eco Toxicity : Ecological Toxicity IDLH :
The Immediately Dangerous to Life and Health
value - This concentration represents a maximum level from which one could escape within 30 minutes without any escape - impairing symptoms or any irreversible health effects. The concentrations are reported in either parts per
UEL (Upper Explosive limit): The lowest concentration limits (normally measured in % volume to air) of a gas or vapour that will be able to support ignition and burn or explode.
million (PPM) or milligrams per cubic metre (mg/m3). TLV-STEL : Short Term Exposure Limit - The concentration to which it is believed that workers can be exposed
LEL (Lower Explosive Limit): The lowest concentration limits
continuously for a short period of time without suffering
(normally measured in % volume to air) of a gas or vapour
from 1) Irritation 2) Chronic or irreversible tissue damage or
that will be able to support ignition and burn or explode.
3) Narcosis of a sufficient degree to increase the likelihood of accidental injury, impair self-rescue or materially reduce
13
14
Notes
15
Notes
15
Issue 1 - January 2014
Gulf Petrochemical Industries Company, (BSC) P.O.Box 26730, Manama, Kingdom of Bahrain Tel: +973 1773 1777 - Fax: +973 1773 1047 Email: gpic@gpic.com Website: www.gpic.com